TW202309242A - Materials for organic electroluminescent devices - Google Patents

Materials for organic electroluminescent devices Download PDF

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TW202309242A
TW202309242A TW111113012A TW111113012A TW202309242A TW 202309242 A TW202309242 A TW 202309242A TW 111113012 A TW111113012 A TW 111113012A TW 111113012 A TW111113012 A TW 111113012A TW 202309242 A TW202309242 A TW 202309242A
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盧分 凌吉
米瑞姆 恩格爾
薩巴斯汀 史托茲
賽巴斯汀 梅爾
雷拉依沙貝爾 羅瑞蓋茲
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德商麥克專利有限公司
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The present invention relates to a composition comprising a compound of formula (H1) and a compound of formula (H2). The present invention furthermore relates to a formulation comprising a composition comprising a compound of formula (H1) and a formula (H2) and a solvent. Finally, the present invention relates to an electronic device comprising a such a composition.

Description

用於有機電致發光裝置之材料Materials for Organic Electroluminescent Devices

本發明關於一種包含式(H1)化合物和式(H2)化合物之組成物。本發明此外關於一種包含組成物和溶劑之調配物，該組成物包含式(H1)和式(H2)之化合物。然後，本發明關於一種包含該種組成物之電子裝置。The present invention relates to a composition comprising a compound of formula (H1) and a compound of formula (H2). The invention furthermore relates to a formulation comprising a composition comprising compounds of formula (H1) and formula (H2) and a solvent. Then, the present invention relates to an electronic device comprising the composition.

用於電子裝置的功能性化合物之開發為目前深入研究的主題。特別地，目的為開發可用其達成改良電子裝置在一或多個相關特徵的性質(諸如，例如，裝置的功率效率和壽命以及發射光的色坐標)之化合物。 根據本發明，術語電子裝置尤其意指有機積體電路(OIC)、有機場效電晶體(OFET)、有機薄膜電晶體(OTFT)、有機發光電晶體(OLET)、有機太陽能電池(OSC)、有機光學檢測器、有機感光器(photoreceptor)、有機場淬滅裝置(OFQD)、有機發光電化學電池(OLEC)、有機雷射二極體(O-雷射)和有機電致發光裝置(OLED)。 特別感興趣的是提供使用於最後提及之稱為OLED的電子裝置之化合物。OLED的一般結構和功能原理為熟習該項技術者已知且描述於例如US 4539507中。 仍然需要關於OLED之性能數據的進一步改良，特別是鑑於廣泛商業用途，例如，用於顯示裝置或作為光源。就此而論，特別重要的是OLED的壽命、效率和操作電壓以及所達成的色值。特別地，在藍光OLED的情況下，關於裝置的效率、壽命和操作電壓之改良是有可能的。 達成該等改良的重要起點為發光體化合物的選擇及主體化合物的選擇。事實上，發光體化合物通常係與第二化合物組合用於發光層，該第二化合物係用作為基質化合物或主體化合物。發光體化合物在本文中意指在電子裝置操作期間發光的化合物。主體化合物在此情況下意指以大於發光體化合物的比例存在於混合物中之化合物。術語基質化合物和術語主體化合物可同義地使用。主體化合物較佳不發射光。即使多種不同的主體化合物存在於發光層的混合物中，彼等個別比例通常大於發光體化合物的比例，或若多種發光體化合物存在於發光層的混合物中，則主體化合物的比例大於個別發光體化合物的比例。例如US 4769292中已描述關於螢光發射層中之該等實施態樣。 若多種化合物的混合物存在於發光層中，則發光體化合物通常是以較小量(即，小於發光層的混合物中存在之其他化合物的比例)存在之組份。在此情況下，發光體化合物亦稱為摻雜劑。 從先前技術中已知的用於螢光發光體之主體化合物為多種化合物。發光層可包含一種或更多種主體化合物。包含氘化和非氘化主體化合物的混合物之主體化合物係從先前技術得知(例如WO 2020/080416中)。 然而，仍然需要用於螢光發光體的其他主體材料或其他主體材料的組合，其可使用於OLED中並且導致在壽命、顏色發射和效率方面具有非常好的性質之OLED。更特別地，需要同時具有非常高的效率、非常好的壽命和非常好的熱穩定性之用於螢光發光體的主體材料或主體材料的組合。 此外，已知OLED可包含不同的層，其可藉由在真空室中的氣相沈積施加或藉由從溶液處理。以氣相沈積為基礎之方法導致良好的結果，但該等方法複雜且昂貴。因此，也需要可從溶液容易且可靠地處理的包含OLED材料之組成物。更特別地，需要包含OLED材料之組成物，其當從調配物(更特別是從溶液如油墨)處理時在製造OLED期間可沉積成均勻之薄膜。在此情況下，該等材料在包含彼的溶液中應具有良好的溶解度，且包含OLED材料之沉積薄膜在用於移除溶劑的乾燥步驟後應儘可能的平滑。重要的是，沉積層形成平滑且均勻的薄膜，因為層厚度不均勻性造成不均勻的發光強度分佈，且膜厚度較薄的區域顯示增加的發光強度，而較厚的區域具有減少的發光強度，其導致OLED的品質下降。同時，包含從溶液處理的薄膜之OLED應呈現良好的性能，例如在壽命、操作電壓和效率方面。 此外仍然需要可得到容易純化和容易處理之穩定的OLED材料之方法。需要以可接受的純度和高產率提供OLED材料之在經濟和品質上令人感興趣之方法。 The development of functional compounds for use in electronic devices is currently the subject of intensive research. In particular, the aim is to develop compounds which can be achieved to improve the properties of electronic devices in one or more relevant features, such as, for example, the power efficiency and lifetime of the device and the color coordinates of the emitted light. According to the present invention, the term electronic device means especially organic integrated circuit (OIC), organic field effect transistor (OFET), organic thin film transistor (OTFT), organic light emitting transistor (OLET), organic solar cell (OSC), Organic optical detectors, organic photoreceptors (photoreceptors), organic field quenching devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs) ). Of particular interest is the provision of compounds for use in the last-mentioned electronic devices known as OLEDs. The general structure and functional principles of OLEDs are known to those skilled in the art and are described, for example, in US 4,539,507. Further refinement of the performance data on OLEDs is still needed, especially in view of widespread commercial use, eg for display devices or as light sources. Of particular importance in this connection are the lifetime, efficiency and operating voltage of the OLEDs as well as the color values achieved. Especially in the case of blue OLEDs improvements are possible with regard to the efficiency, lifetime and operating voltage of the device. An important starting point for achieving these improvements is the selection of the emitter compound and the selection of the host compound. In fact, the emitter compound is usually used in the light-emitting layer in combination with a second compound which acts as matrix compound or host compound. An emitter compound here means a compound that emits light during operation of the electronic device. A host compound in this case means a compound which is present in the mixture in a larger proportion than the emitter compound. The term matrix compound and the term host compound may be used synonymously. The host compound preferably does not emit light. Even if a plurality of different host compounds are present in the mixture of the emitting layer, their individual proportions are generally greater than the proportions of the emitter compounds, or if a plurality of emitter compounds are present in the mixture of the emitting layer, the proportion of the host compounds is greater than that of the individual emitter compounds proportion. Such implementations in fluorescent emissive layers have been described, for example, in US 4769292. If a mixture of compounds is present in the light-emitting layer, the emitter compound is usually a component present in a minor amount (ie, in a smaller proportion than the other compounds present in the mixture of the light-emitting layer). In this case, the emitter compounds are also referred to as dopants. Host compounds for fluorescent emitters are known from the prior art in a wide variety of compounds. The light emitting layer may contain one or more host compounds. Host compounds comprising mixtures of deuterated and non-deuterated host compounds are known from the prior art (eg in WO 2020/080416). However, there is still a need for other host materials or other combinations of host materials for fluorescent emitters, which can be used in OLEDs and lead to OLEDs with very good properties in terms of lifetime, color emission and efficiency. More particularly, there is a need for host materials or combinations of host materials for fluorescent emitters that simultaneously have very high efficiencies, very good lifetimes and very good thermal stability. Furthermore, it is known that OLEDs can comprise different layers, which can be applied by vapor deposition in a vacuum chamber or by processing from solution. Methods based on vapor deposition lead to good results, but are complex and expensive. Accordingly, there is also a need for compositions comprising OLED materials that can be easily and reliably processed from solution. More particularly, there is a need for compositions comprising OLED materials that can be deposited as uniform thin films during the manufacture of OLEDs when processed from formulations, more particularly from solutions such as inks. In this case, the materials should have good solubility in solutions containing them, and the deposited film containing OLED materials should be as smooth as possible after the drying step for solvent removal. It is important that the deposited layer forms a smooth and uniform film because layer thickness inhomogeneity causes a non-uniform luminous intensity distribution, and regions with thinner film thicknesses show increased luminous intensity, while thicker regions have decreased luminous intensity , which leads to a decrease in the quality of the OLED. At the same time, OLEDs comprising thin films processed from solution should exhibit good properties, eg in terms of lifetime, operating voltage and efficiency. Furthermore, there is still a need for methods that can lead to stable OLED materials that are easy to purify and easy to handle. There is a need for an economically and qualitatively interesting method of providing OLED materials with acceptable purity and high yield.

本發明因此係基於提供適合用於電子裝置(諸如OLED)，更特別是作為螢光發光體之基質組份的包含OLED材料之組成物的技術目標。本發明亦是基於提供特別適合使用於溶液處理的包含OLED材料之組成物的技術目標。本發明亦基於提供方法的技術目標。 在對用於電子裝置之新穎組成物之研究中，目前已發現，如下所定義之包含式(H1)化合物和式(H2)化合物之組成物非常適合使用於電子裝置。特別地，彼等可達成上述技術目標之一或多者，較佳為全部。 本申請案因此關於一種組成物，其包含： 式(H1)之第一主體材料，

Figure 02_image001
式(H2)之第二主體材料，
Figure 02_image003
及摻雜劑材料； 其中下列適用於所使用的符號和標號： G 1為具有6至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R X取代； G 2係選自式(G2)之基團：
Figure 02_image005
其中基團E為選自下列之二價橋；-Y=Y-、-C(R B0) 2-、Si(R B0) 2-、-O-、-S-、-C(=O)-、-S(=O)-、-SO 2-、-BR B0-、-N(R B0)-或-P(R B0)-，較佳為-Y=Y-、-C(R B0) 2-、-O-、-S-；及其中R B0在每次出現時相同或不同地代表H、F、CN、具有1至40個C原子之直鏈烷基或具有3至40個C原子之支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)；其中二個相鄰的取代基R B0可形成單環或多環的脂族環系統或芳族環系統，其可經一或多個基團R取代； Y    在每次出現時相同或不同地代表C-R Y或N；其先決條件為當Y鍵結至基團Ant 2時，Y代表C； Ant 1為式(A1)之基團：
Figure 02_image007
其中式(A1)中之虛線鍵表示至基團G 1的鍵結位置，及其中基團Ant 1可鍵結至G 1的任何自由位置； Ant 2為式(A2)之基團：
Figure 02_image009
其中式(A2)中之虛線鍵表示至基團G 2的鍵結位置，及其中基團Ant 2可鍵結至G 2的任何自由位置； Ar A1、Ar B1、Ar AS、Ar BS在每次出現時相同或不同地為具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R取代； R A1至R A8、R B1至R B8、R Y、R X在每次出現時相同或不同地代表選自下列之基團：H、D、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R) 2、N(Ar) 2、NO 2、Si(R) 3、B(OR) 2、OSO 2R、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基(thioalkyl)或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、Si(R) 2、Ge(R) 2、Sn(R) 2、C=O、C=S、C=Se、P(=O)(R)、SO、SO 2、O、S或CONR置換及其中一或多個H原子可經D、F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)、和具有5至60個芳族環原子之芳氧基(其可經一或多個基團R取代)； 其先決條件為R B1至R B8和R Y不代表D；及其中二個相鄰的基團R A1至R A8、R B1至R B8、R Y或R X可一起形成脂族、芳族或雜芳族環系統，其可經一或多個基團R取代； R       在每次出現時相同或不同地代表H、D、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R’) 2、N(Ar) 2、NO 2、Si(R’) 3、B(OR’) 2、OSO 2R’、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R’取代，其中在各情況下一或多個非相鄰的CH 2基團可經R’C=CR’、C≡C、Si(R’) 2、Ge(R’) 2、Sn(R’) 2、C=O、C=S、C=Se、P(=O)(R’)、SO、SO 2、O、S或CONR’置換及其中一或多個H原子可經D、F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R’取代)、或具有5至60個芳族環原子之芳氧基(其可經一或多個基團R’取代)；其中二個相鄰的取代基R可一起形成脂族或芳族環系統，其可經一或多個基團R’取代； Ar      在每次出現時相同或不同地為具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R’取代； R’    在每次出現時相同或不同地代表H、D、F、Cl、Br、I、CN、具有1至20個C原子之直鏈烷基、烷氧基或烷硫基或具有3至20個C原子之支鏈或環狀烷基、烷氧基、或烷硫基(其中在各情況下一或多個非相鄰的CH 2基團可經SO、SO 2、O、S置換及其中一或多個H原子可經D、F、Cl、Br或I置換)、或具有5至24個芳族環原子之芳族或雜芳族環系統；及 n       在每次出現時相同或不同地為0或1；其中當n為0時，則對應Ar AS或Ar BS不存在，及蒽基係直接鍵結至基團G 1或G 2； m為0或1； 其特徵在於式(H1)化合物包含至少一個氘原子，及式(H2)化合物實質上不含氘原子。 更佳地，式(H2)化合物不含氘原子。因此，在式(H2)化合物中基團R和R’不代表氘原子。 氘原子在此也稱為“D”。 此外，下列化學基團的定義適用於本申請案之目的： 芳基就本發明之意義而言含有6至60個芳族環原子，較佳6至40個芳族環原子，更佳6至20個芳族環原子；雜芳基就本發明之意義而言含有5至60個芳族環原子，較佳5至40個芳族環原子，更佳5至20個芳族環原子，其中至少一者為雜原子。雜原子較佳地係選自N、O和S。此表示基本定義。若在本發明說明中表示其他較佳選擇，例如有關所存在之芳族環原子或雜原子的數目，則這些適用。 芳基或雜芳基在此意指簡單芳族環，即苯，或簡單雜芳族環，例如吡啶、嘧啶或噻吩，或縮合(稠合(annellated))芳族或雜芳族多環，例如萘、菲、喹啉或咔唑。縮合(稠合)芳族或雜芳族多環就本申請案的意義而言係由二或更多個彼此縮合之簡單芳族或雜芳族環組成。 在各情況下可經上述基團取代且可經由任何所要位置連接至芳族或雜芳族環系統之芳基或雜芳基特別意指衍生自下列之基團：苯、萘、蒽、菲、芘、二氫芘、
Figure 111113012-001
(chrysene)、苝、丙二烯合茀(fluoranthene)、苯并蒽、苯并菲、稠四苯、稠五苯、苯并芘、呋喃、苯并呋喃、異苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、異苯并噻吩、二苯并噻吩、吡咯、吲哚、異吲哚、咔唑、吡啶、喹啉、異喹啉、吖啶、啡啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、啡噻𠯤、啡㗁𠯤、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑(naphthimidazole)、菲并咪唑(phenanthrimidazole)、吡啶并咪唑(pyridimidazole)、吡𠯤并咪唑(pyrazinimidazole)、喹㗁啉并咪唑(quinoxalinimidazole)、㗁唑、苯并㗁唑、萘并㗁唑(naphthoxazole)、蒽并㗁唑(anthroxazole)、菲并㗁唑(phenanthroxazole)、異㗁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、嗒𠯤、苯并嗒𠯤、嘧啶、苯并嘧啶、喹㗁啉、吡𠯤、啡𠯤、㖠啶、氮雜咔唑、苯并咔啉、啡啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-㗁二唑、1,2,4-㗁二唑、1,2,5-㗁二唑、1,3,4-㗁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三𠯤、1,2,4-三𠯤、1,2,3-三𠯤、四唑、1,2,4,5-四𠯤、1,2,3,4-四𠯤、1,2,3,5-四𠯤、嘌呤、蝶啶、吲
Figure 111113012-002
及苯并噻二唑。 根據本發明之定義的芳氧基意指經由氧原子鍵結的如上述所定義之芳基。類似定義適用於雜芳氧基。 芳族環系統就本發明之意義而言在環系統中含有6至60個C原子，較佳地6至40個C原子，更佳地6至20個C原子。雜芳族環系統就本發明之意義而言含有5至60個芳族環原子，較佳地5至40個芳族環原子，更佳地5至20個芳族環原子，其中至少一個為雜原子。雜原子較佳選自N、O及/或S。芳族或雜芳族環系統就本發明之意義而言意指不一定只含有芳基或雜芳基，而是其中此外多個芳基或雜芳基可藉由非芳族單元(較佳為少於10%之非H的原子)(諸如，例如sp 3-混成之C、Si、N或O原子、sp 2-混成之C或N原子或sp-混成之C原子)連接的系統。因此，例如，系統諸如9,9’-螺二茀、9,9’-二芳基茀、三芳基胺、二芳基醚、二苯乙烯、等等亦意欲為就本發明之意義而言的芳族環系統，如為其中二或多個芳基例如藉由直鏈或環狀烷基、烯基或炔基或藉由矽基連接之系統。此外，其中二或多個芳基或雜芳基係經由單鍵彼此連結之系統亦為就本發明之意義而言的芳族或雜芳族環系統，諸如，例如系統諸如聯苯、聯三苯或二苯基三𠯤。 在各情況下亦可經如上述所定義之基團取代且可經由任何所要位置連接至芳族或雜芳族基團之具有5至60個芳族環原子的芳族或雜芳族環系統特別意指衍生自下列之基團：苯、萘、蒽、苯并蒽、菲、苯并菲、芘、
Figure 111113012-001
(chrysene)、苝、丙二烯合茀(fluoranthene)、稠四苯、稠五苯、苯并芘、聯苯、伸聯苯(biphenylene)、聯三苯(terphenyl)、聯伸三苯(terphenylene)、聯四苯(quaterphenyl)、茀、螺二茀、二氫菲、二氫芘、四氫芘、順-或反-茚并茀、三聚茚(truxene)、異三聚茚(isotruxene)、螺三聚茚、螺異三聚茚、呋喃、苯并呋喃、異苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、異苯并噻吩、二苯并噻吩、吡咯、吲哚、異吲哚、咔唑、吲哚并咔唑、茚并咔唑、吡啶、喹啉、異喹啉、吖啶、啡啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、啡噻𠯤、啡㗁𠯤、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑(naphthimidazole)、菲并咪唑(phenanthrimidazole)、吡啶并咪唑(pyridimidazole)、吡𠯤并咪唑(pyrazinimidazole)、喹㗁啉并咪唑(quinoxalinimidazole)、㗁唑、苯并㗁唑、萘并㗁唑(naphthoxazole)、蒽并㗁唑(anthroxazole)、菲并㗁唑(phenanthroxazole)、異㗁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、嗒𠯤、苯并嗒𠯤、嘧啶、苯并嘧啶、喹㗁啉、1,5-二氮雜蒽、2,7-二氮雜芘、2,3-二氮雜芘、1,6-二氮雜芘、1,8-二氮雜芘、4,5-二氮雜芘、4,5,9,10-四氮雜苝、吡𠯤、啡𠯤、啡㗁𠯤、啡噻𠯤、螢紅環(fluorubin)、㖠啶、氮雜咔唑、苯并咔啉、啡啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-㗁二唑、1,2,4-㗁二唑、1,2,5-㗁二唑、1,3,4-㗁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三𠯤、1,2,4-三𠯤、1,2,3-三𠯤、四唑、1,2,4,5-四𠯤、1,2,3,4-四𠯤、1,2,3,5-四𠯤、嘌呤、喋啶、吲
Figure 111113012-002
和苯并噻二唑、或這些基團的組合。 就本發明之目的而言，具有1至40個C原子之直鏈烷基或具有3至40個C原子之支鏈或環狀烷基或具有2至40個C原子之烯基或炔基，其中，此外，個別H原子或CH 2基團可經在上述該等基團定義下之基團取代，較佳意指基團甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、2-甲基丁基、正戊基、二級戊基、環戊基、新戊基、正己基、環己基、新己基、正庚基、環庚基、正辛基、環辛基、2-乙基己基、三氟甲基、五氟乙基、2,2,2-三氟乙基、乙烯基、丙烯基、丁烯基、戊烯基、環戊烯基、己烯基、環己烯基、庚烯基、環庚烯基、辛烯基、環辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基或辛炔基。具有1至40個C原子之烷氧基或烷硫基較佳意指甲氧基、三氟甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、二級丁氧基、三級丁氧基、正戊氧基、二級戊氧基、2-甲基丁氧基、正己氧基、環己氧基、正庚氧基、環庚氧基、正辛氧基、環辛氧基、2-乙基己氧基、五氟乙氧基、2,2,2-三氟乙氧基、甲硫基、乙硫基、正丙硫基、異丙硫基、正丁硫基、異丁硫基、二級丁硫基、三級丁硫基、正戊硫基、二級戊硫基、正己硫基、環己硫基、正庚硫基、環庚硫基、正辛硫基、環辛硫基、2-乙基己硫基、三氟甲硫基、五氟乙硫基、2,2,2-三氟乙硫基、乙烯硫基、丙烯硫基、丁烯硫基、戊烯硫基、環戊烯硫基、己烯硫基、環己烯硫基、庚烯硫基、環庚烯硫基、辛烯硫基、環辛烯硫基、乙炔硫基、丙炔硫基、丁炔硫基、戊炔硫基、己炔硫基、庚炔硫基或辛炔硫基。 就本申請案之目的而言，二或更多個基團彼此可形成環之規則特別意指：二個基團以一化學彼此鍵鍵聯。此以下列圖解說明：
Figure 02_image011
然而，此外，上述規則也意指：在其中二基團之一表示氫的情況中，第二基團鍵結於氫原子所鍵結之位置，且形成環。此以下列圖解說明：
Figure 02_image013
當二個基團彼此形成環時，則較佳的是二個基團為相鄰的基團。相鄰基團就本發明之意義而言為鍵結至彼此直接連接的原子或鍵結至同一原子上的基團。 根據一較佳實施態樣，式(H1)化合物之分子量(Mw)為Mw≥350 g/mol，較佳為Mw≥380 g/mol，更佳為Mw≥400 g/mol，甚至更佳為Mw≥450 g/mol。 再者，較佳的是基團G 1係選自下列式中之一者所示的基團：
Figure 02_image015
Figure 02_image017
其中： X       在每次出現時相同或不同地代表C-R X或N；其先決條件為當X鍵結至基團Ant 1時，X代表C； E 1、E 2、E 3、E 4在每次出現時相同或不同地代表單鍵、-BR 0-、-C(R 0) 2-、-Si(R 0) 2-、-C(=O)-、-O-、-S-、 -S(=O)-、-SO 2-、-N(R 0)-或-P(R 0)-；其先決條件為基團E 1和E 3中只有一者可為單鍵，及基團E 4和E 2中只有一者可為單鍵； E 5代表-BR 0-、-C(R 0) 2-、-Si(R 0) 2-、-C(=O)-、 -O-、-S-、-S(=O)-、-SO 2-、-N(R 0)-或-P(R 0)- ，較佳代表-C(R 0) 2-、-O-或-S-，更佳代表-O-或-S-； R 0在每次出現時相同或不同地代表H、D、F、CN、具有1至40個(較佳為1至20個，更佳為1至10個)C原子之直鏈烷基或具有3至40個(較佳為3至20個，更佳為3至10個)C原子之支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至60個(較佳為5至40個，更佳地5至30個，甚至更佳地6至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)；其中二個相鄰的取代基R 0可形成單環或多環的脂族環系統或芳族環系統，其可經一或多個基團R取代； R X、R 具有與上述相同的定義。 較佳地，E 1、E 2、E 3、E 4在每次出現時相同或不同地代表單鍵、-O-或-S-；其先決條件為基團E 1和E 3中之一者為單鍵而另一個基團為-O-或-S-，及基團E 4和E 2中之一者為單鍵而另一基團為-O-或-S-。更佳地，E 1和E 2代表-O-或-S-且E 3和E 4代表單鍵。 式(G1-1)至(G1-12)之結構中，下列結構為較佳：(G1-1)、(G1-3)、(G1-4)、(G1-5)、(G1-7)、(G1-9)、(G1-10)、(G1-11)和(G1-12)。下列結構為特佳：(G1-1)、(G1-3)、(G1-4)、(G1-5,) (G1-9)、(G1-10)。 較佳地，式(H1)化合物係選自下列式之化合物：
Figure 02_image019
Figure 02_image021
Figure 02_image023
Figure 02_image025
其中該等符號具有與上述相同的意義及其中式(G1-1-1)至(G1-12-3)之化合物包含至少一個氘原子。 主體材料(H1)較佳係選自式(G1-1-1)、(G1-2-1)、(G1-3-1)、(G1-4-1)、(G1-4-2)、(G1-5-1)、(G1-6-1)、(G1-7-1)、(G1-8-1)、(G1-9-1)、(G1-9-3)、(G1-10-1)、(G1-10-3)、(G1-11-1)、(G1-11-3)、(G1-12-1)、(G1-12-3) 之化合物。主體材料(H1)非常佳係選自式(G1-1-1)、(G1-3-1)、(G1-4-1)、(G1-4-2)、(G1-5-1)、(G1-7-1) (G1-9-1)、(G1-10-1)、(G1-11-1)和(G1-12-1)之化合物。 根據一較佳實施態樣，式(H1)中之標號m等於0，和式(H1)之第一主體化合物僅包含一個基團Ant 1。 基團(G1-1)至(G1-10)上的鍵結位置可編號如下：
Figure 02_image027
Figure 02_image029
Figure 02_image031
Figure 02_image033
Figure 02_image035
Figure 02_image037
基團Ant 1之適當鍵結位置的實例係如下表所示：
Figure 02_image039
Figure 02_image041
符號“-”表示沒有第二基團Ant 1。式(G1-1-1)至(G1-12-6)之中，化合物(G1-1-1)、(G1-1-2)、(G1-1-4)、(G1-2-3)、(G1-2-4)、(G1-2-7)、(G1-3-1)、(G1-3-3)、(G1-4-2)、(G1-4-3)、(G1-4-4)、(G1-4-12)、(G1-4-13)、(G1-5-2)、(G1-5-3)、(G1-5-4)、(G1-5-14)、(G1-5-12)、(G1-5-17)、(G1-6-1)、(G1-7-1)、(G1-7-2)、(G1-7-3)、(G1-7-5)、(G1-8-1)、(G1-8-2)、(G1-8-3)、(G1-8-7)、(G1-8-9)、(G1-9-1)、(G1-9-3)、(G1-9-5)、(G1-10-1)、(G1-10-3)、(G1-10-7)、(G1-11-2)、(G1-11-6)、(G1-11-5)、(G1-12-1)為較佳，其中第二基團Ant 1不存在的化合物(G1-4-12)為更佳。下列基團為非常佳的：(G1-1-1)、(G1-1-2)、(G1-2-3)、(G1-2-4)、(G1-3-1)、(G1-4-2)、(G1-4-3)、(G1-4-4)、(G1-5-2)、(G1-5-3)、(G1-5-4)、(G1-7-1)、(G1-7-2)、(G1-8-1)、(G1-8-2)、(G1-8-3)、(G1-9-1)、(G1-10-1)、(G1-12-1)。 較佳地，基團Ar A1和Ar B1在每次出現時係相同或不同地選自由下列所組成之群組：苯基、聯苯、聯三苯(terphenyl)、聯四苯(quaterphenyl)、茀、螺二茀、萘、蒽、菲、聯伸三苯(triphenylene)、丙二烯合茀(fluoranthene)、稠四苯、
Figure 111113012-001
(chrysene)、苯并蒽、苯并菲、芘或苝、二苯并呋喃、咔唑和二苯并噻吩，彼等各自可經一或多個基團R取代在任何自由位置；及其中Ar A1、Ar B1也可為上述基團中之二或更多者的組合。更佳地，基團Ar A1和Ar B1在每次出現時係相同或不同地選自由下列所組成之群組：苯基、聯苯、聯三苯、聯四苯、萘、菲，彼等各自可經一或多個基團R取代在任何自由位置。 較佳地，基團Ant 1為式(A1-1)至(A1-5)中之一者的基團：
Figure 02_image043
Figure 02_image045
Figure 02_image047
Figure 02_image049
Figure 02_image051
其中式(A1-1)至(A1-5)中之虛線鍵表示至基團G 1的鍵結位置，其中基團Ant 1可鍵結至G 1的任何自由位置；及其中 R A9至R A21在每次出現時相同或不同地代表選自下列之基團：H、D、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R) 2、N(Ar) 2、NO 2、Si(R) 3、B(OR) 2、OSO 2R、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基(thioalkyl)或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、Si(R) 2、Ge(R) 2、Sn(R) 2、C=O、C=S、C=Se、P(=O)(R)、SO、SO 2、O、S或CONR置換及其中一或多個H原子可經D、F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)、和具有5至60個芳族環原子之芳氧基(其可經一或多個基團R取代)；其中二個相鄰的基團R A9至R A21可一起形成脂族、芳族或雜芳族環系統，其可經一或多個基團R取代。 較佳地，R A1至R A8在每次出現時相同或不同地代表H、D、F、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、O或S置換及其中一或多個H原子可經D或F置換)、具有5至60個(較佳5至40個，更佳5至30個，特佳5至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。更佳地，R A1至R A8在每次出現時相同或不同地代表H、D、F、具有1至20個(較佳1至10個，更佳1至6個) C原子之直鏈烷基或具有3至20個(較佳3至10個，更佳3至6個) C原子的支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至40個(較佳5至30個，更佳5至18個)芳族環原子的芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。特佳地，R A1至R A8係選自H和D。 較佳地，R A9至R A21在每次出現時相同或不同地代表H、D、F、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、O或S置換及其中一或多個H原子可經D或F置換)、具有5至60個(較佳5至40個，更佳5至30個，特佳5至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。更佳地，R A9至R A21在每次出現時相同或不同地代表H、D、F、具有1至20個(較佳1至10個，更佳1至6個) C原子之直鏈烷基或具有3至20個(較佳3至10個，更佳3至6個) C原子的支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至40個(較佳5至30個，更佳5至18個)芳族環原子的芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。特佳地，R A9至R A21係選自H和D。 更佳地，基團Ant 1為式(A1-1-D)至(A1-5-D)中之一者的基團：
Figure 02_image053
Figure 02_image055
Figure 02_image057
其中 x    為選自從0至8(更佳地從1至8)之整數； y1 為選自從0至5(更佳地從1至5)之整數； y2 為選自從0至4(更佳地從1至4)之整數； y3 為選自從0至3(更佳地從1至3)之整數； z    為選自從0至7(更佳地從1至7)之整數。 例如，若標號x代表8，則式(A1-1-D)中之蒽基團包含8個氘化原子，其意指式(A1-1-D)中之蒽基團完全被氘化。 如上所述，式(H1)化合物包含至少一個氘原子。至少一個氘原子可為基團Ant 1或G 1上之取代基。 根據一較佳實施態樣，該至少一個氘原子為基團Ant 1上之取代基。 當該至少一個氘原子為基團Ant 1上之取代基時，較佳的是： -  在式(A1)中：至少一個基團R A1至R A8代表氘原子或基團Ar A1中至少一個基團R代表氘原子； -  在式(A1-1)至(A1-5)中：至少一個基團R A1至R A8代表氘原子或至少一個基團R A9至R A21代表氘原子； -  在式(A1-1-D)至(A1-5-D)中：存在於式中之至少一個選自x、y1、y2、y3和z之標號不等於0。 根據一較佳實施態樣，該至少一個氘原子為基團G 1上之取代基。 在此情況下，較佳的是至少一個基團R X代表氘原子。更特別地，較佳的是至少10%的存在於基團G 1中之取代基R X代表氘原子。更佳地，至少20%的存在於基團G 1中之取代基R X代表氘原子，或至少30%的存在於基團G 1中之取代基R X代表氘原子，或至少40%的存在於基團G 1中之取代基R X代表氘原子，或至少50%的存在於基團G 1中之取代基R X代表氘原子，或至少60%的存在於基團G 1中之取代基R X代表氘原子，或至少70%的存在於基團G 1中之取代基R X代表氘原子，或至少80%的存在於基團G 1中之取代基R X代表氘原子，或至少90%的存在於基團G 1中之取代基R X代表氘原子。 較佳地，R X在每次出現時相同或不同地代表H、D、F、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、O或S置換及其中一或多個H原子可經D或F置換)、具有5至60個(較佳5至40個，更佳5至30個，特佳5至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。更佳地，R X在每次出現時相同或不同地代表H、D、F、具有1至20個(較佳1至10個，更佳1至6個) C原子之直鏈烷基或具有3至20個(較佳3至10個，更佳3至6個) C原子的支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至40個(較佳5至30個，更佳5至18個)芳族環原子的芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。更佳地，R X係選自H和D。 特佳的是式(H1)化合物係以氘原子氘化至少10%，而該氘原子係為基團G 1上、基團Ant 1上或基團G 1和Ant 1二者上之取代基。此意指式(H1)化合物中之至少10%的可用氫原子經氘原子置換。更佳地，式(H1)化合物係至少20%氘化，或至少30%氘化，或至少40%氘化，或至少50%氘化，或至少60%氘化，或至少70%氘化，或至少80%氘化，或至少90%氘化。 非常佳之式(H1)化合物的實例係顯示於下表中：
Figure 02_image059
Figure 02_image061
Figure 02_image063
Figure 02_image065
Figure 02_image067
Figure 02_image069
在結構中，例如，術語“D8”或“D4”意指對應環分別經8個、4個氘原子取代。 較佳地，基團G 2係選自下列式中之一者所示的基團：
Figure 02_image071
其中： Y    在每次出現時相同或不同地代表C-R Y或N；其先決條件為當Y鍵結至基團Ant 2時，Y代表C；及其中該等符號R Y具有與上述相同的意義；及 R B0具有與上述相同的意義。 較佳地，R B0在每次出現時相同或不同地代表H, a具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至40個(較佳5至20個，更佳6至18個)芳族環原子的芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)；其中二個相鄰的取代基R B0可形成單環或多環的脂族環系統或芳族環系統，其可經一或多個基團R取代。 基團(G2-1)至(G2-5)之中，基團(G2-1)和(G2-2)為較佳。 較佳地，式(H2)化合物係選自下列式之基團：
Figure 02_image073
Figure 02_image075
其中該等符號具有與上述相同的定義。 式(G2-1-1)至(G2-5-2)化合物之中，下列化合物為較佳：(G2-1-1)、(G2-2-1)、(G2-4-1)、(G2-5-1)、(G2-5-2)，更佳為(G2-1-1)、(G2-2-1)、(G2-5-1)、(G2-5-2)，及非常佳為(G2-1-1)、(G2-2-1)。 基團(G2-1)至(G2-5)上之鍵結位置可編號如下：
Figure 02_image077
Figure 02_image079
Figure 02_image081
基團Ant 2之較佳鍵結位置係表示於下表中：
Figure 02_image083
Figure 02_image085
式(G2-1-1)至(G2-5-20)化合物之中，下列化合物為較佳：(G2-1-6)、(G2-1-7)、(G2-1-9)、(G2-1-10)、(G2-1-11)、(G2-1-12)、(G2-2-7)、(G2-2-8)、(G2-2-9)、(G2-2-10)、(G2-3-7)、(G2-3-8)、(G2-3-9)、(G2-4-5)、(G2-4-7)、(G2-5-5)、(G2-5-7)、(G2-5-15)、(G2-5-17)和(G2-5-20)。下列式之化合物為甚至更佳：(G2-1-6)、(G2-1-9)、(G2-2-8)、(G2-2-9)、(G2-4-7)、(G2-5-7)、(G2-5-15)和(G2-5-20)。 較佳地，R Y在每次出現時相同或不同地代表H、F、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、O 或S置換及其中一或多個H原子可經D或F置換)、具有5至60個(較佳5至40個，更佳5至30個，特佳5至18個)芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R取代。更佳地，R Y在每次出現時相同或不同地代表H、F、具有1至20個(較佳1至10個，更佳1至6個) C原子之直鏈烷基或具有3至20個(較佳3至10個，更佳3至6個) C原子的支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至40個(較佳5至30個，更佳5至18個)芳族環原子的芳族或雜芳族環系統，其在各情況下可經一或多個基團R取代。更佳地，R Y代表H。 基團Ant 2較佳為式(A2-1)至(A2-5)中之一者的基團：
Figure 02_image087
Figure 02_image089
Figure 02_image091
Figure 02_image093
Figure 02_image095
其中式(A2-1)至(A2-5) 中之虛線鍵表示至基團G 2的鍵結位置，及其中基團Ant 2可鍵結至G 2的任何自由位置；及其中 R B9至R B21在每次出現時相同或不同地代表選自下列之基團：H、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R) 2、N(Ar) 2、NO 2、Si(R) 3、B(OR) 2、OSO 2R、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基(thioalkyl)或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、Si(R) 2、Ge(R) 2、Sn(R) 2、C=O、C=S、C=Se、P(=O)(R)、SO、SO 2、O、S或CONR置換及其中一或多個H原子可經F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)、和具有5至60個芳族環原子之芳氧基(其可經一或多個基團R取代)之整數；其中R B9至R B21之中二個相鄰的基團可一起形成脂族、芳族或雜芳族環系統，其可經一或多個基團R取代。 較佳地，R B1至R B8在每次出現時相同或不同地代表H、F、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代)、具有5至60個(較佳5至40個，更佳5至30個，特佳5至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。更佳地，R B1至R B8在每次出現時相同或不同地代表H、F、具有1至20個(較佳1至10個，更佳1至6個) C原子之直鏈烷基或具有3至20個(較佳3至10個，更佳3至6個) C原子的支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至40個(較佳5至30個，更佳5至18個)芳族環原子的芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。特佳地，R B1至R B8代表H。 較佳地，R B9至R B21在每次出現時相同或不同地代表H、F、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代)、具有5至60個(較佳5至40個，更佳5至30個，特佳5至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。更佳地，R B9至R B21在每次出現時相同或不同地代表H、F、具有1至20個(較佳1至10個，更佳1至6個) C原子之直鏈烷基或具有3至20個(較佳3至10個，更佳3至6個) C原子的支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至40個(較佳5至30個，更佳5至18個)芳族環原子的芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)。 非常佳之式(H2)化合物的實例係顯示於下表中：
Figure 02_image097
Figure 02_image099
Figure 02_image101
較佳地，基團AR AS和AR BS在每次出現時相同或不同地代表苯基、聯苯、茀、螺二茀、萘、菲、蒽、二苯并呋喃、二苯并噻吩、咔唑、吡啶、嘧啶、吡𠯤、嗒𠯤、三𠯤、苯并吡啶、苯并嗒𠯤、苯并嘧啶和喹唑啉，彼等各自可經一或多個基團R取代。更佳地，基團AR AS和AR BS在每次出現時相同或不同地代表苯基、聯苯或萘，彼等各自可經一或多個基團R取代。 較佳地，R在每次出現時相同或不同地代表H、D、F、CN、N(Ar) 2、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R’取代，其中在各情況下一或多個非相鄰的CH 2基團可經R’C=CR’、C≡C、O或S置換及其中一或多個H原子可經D或F置換)、或具有5至60個(較佳5至40個，更佳5至30個，特佳6至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R’取代)。 較佳地，Ar在每次出現時相同或不同地為具有5至40個(較佳5至30個，更佳5至25個，非常更佳6至18個)芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R’取代； 較佳地，R’在每次出現時相同或不同地代表H、D，F、Cl、Br、I、CN、具有1至10個C原子之直鏈烷基或具有3至10個C原子之支鏈或環狀烷基(其中在各情況下一或多個H原子可經D或F置換)、或具有5至18個C原子之芳族或雜芳族環系統。 根據本發明，組成物包含式(H1)之第一主體材料、式(H2)之第二主體材料和摻雜劑材料。摻雜劑材料較佳為螢光發光體。 較佳地，組成物包含至少一種螢光發光體，其包含下列基團中之至少一者： - 含有三個直接鍵結至氮的經取代或未經取代之芳族或雜芳族環系統的芳基胺； - 橋聯三芳基胺； - 具有至少14個芳族環原子之縮合芳族或雜芳族環系統； - 茚并茀、茚并茀胺或茚并茀二胺； - 苯并茚并茀、苯并茚并茀胺或苯并茚并茀二胺； - 二苯并茚并茀、二苯并茚并茀胺或二苯并茚并茀二胺； - 含有具有至少10個芳族環原子的縮合芳基之茚并茀； - 雙茚并茚并茀； - 茚并二苯并呋喃；茚并茀胺或茚并茀二胺； - 茀二聚物； - 啡㗁𠯤；或 - 硼衍生物。 更佳地，組成物包含至少一種如下所述的下列式(E-1)、(E-2)、(E-3)或E-4)中之一者的螢光發光體：
Figure 02_image103
其中 Ar 10、Ar 11、Ar 12在每次出現時相同或不同地為具有6至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R取代；其先決條件為至少一個基團Ar 10、Ar 11、Ar 12為具有10至40個芳族環原子之芳族或雜芳族環系統且含有至少一個由2至4個彼此縮合的芳族環組成的縮合芳基或雜芳基，其中該芳族或雜芳族環系統可經一或多個基團R取代； R      具有與上述相同的定義；及 e       為1、2、3或4；更佳地，e為1；
Figure 02_image105
其中 Ar 20、Ar 21、Ar 22在每次出現時相同或不同地為具有6至30個芳族環原子之芳基或雜芳基，其在各情況下亦可經一或多個基團R取代； E 20在每次出現時係相同或不同地選自BR、C(R 0) 2、Si(R 0) 2、C=O、C=NR 0、C=C(R 0) 2、O、S、S=O、SO 2、NR 0、PR 0、P(=O)R 0或P(=S)R 0；其中Ar 20、Ar 21和E 20一起形成五員環或六員環，及Ar 21、Ar 22和E 20一起形成五員環或六員環； R 0在每次出現時相同或不同地代表H、D、F、具有1至20個(較佳1至10個) C原子之直鏈烷基或具有3至20個(較佳為3至10個) C原子之支鏈或環狀烷基(彼等各自可經一或多個R基團取代，其中在各情況下一或多個非相鄰的CH 2基團可經O或S置換和其中一或多個H原子可經D或F置換)、或具有5至40個(較佳為5至30個，更佳為6至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)，其中兩個相鄰的基團R 0可一起形成脂族或芳族環系統，其可經一或多個基團R取代， R      具有與上述相同的定義； p、q   在每次出現時相同或不同地為0或1，其先決條件為p+q=1； r  為1、2或3；
Figure 02_image107
其中 Ar 30、Ar 31、Ar 32在每次出現時相同或不同地代表具有5至22個(較佳5至18個，更佳6至14個)芳族環原子之經取代或未經取代之芳基或雜芳基； E 30代表B或N； E 31、E 32、E 33在每次出現時相同或不同地代表O、S、C(R 0) 2、C=O、C=S、C=NR 0、C=C(R 0) 2、Si(R 0) 2、BR 0、NR 0、PR 0、SO 2、SeO 2或化學鍵，其先決條件為若E 30為B，則基團E 31、E 32、E 33中之至少一者代表NR 0，及若E 30為N，則基團E 31、E 32、E 33中之至少一者代表BR 0； R 0具有與上述相同的定義； s、t、u 在每次出現時相同或不同地為0或1，其先決條件為s+t+u≥1。
Figure 02_image109
其中 Ar 40、Ar 41、Ar 42在每次出現時相同或不同地代表具有5至22個(較佳5至18個，更佳6至14個)芳族環原子之經取代或未經取代之芳基或雜芳基； E 41、E 42、E 43在每次出現時相同或不同地代表O、S、C(R 0) 2、C=O、C=S、C=NR 0、C=C(R 0) 2、Si(R 0) 2、BR 0、NR 0、PR 0、SO 2、SeO 2或化學鍵，其先決條件為基團E 41、E 42、E 43中之至少一者存在且代表化學鍵； R 0具有與上述相同的定義； i、g、h 在每次出現時相同或不同地為0或1，其先決條件為i+g+h≥1。 較佳地，式(E-1)之螢光發光體包含至少一個基團Ar 10、Ar 11或Ar 12，較佳為Ar 10，而其係選自式(Ar 10-1)至(Ar 10-24)之基團：
Figure 02_image111
Figure 02_image113
Figure 02_image115
其中基團Ar 10-1至Ar 10-24可經一或多個基團R取代在所有自由位置；及其中 E 10在每次出現時係相同或不同地選自BR 0、C(R 0) 2、Si(R 0) 2、C=O、C=NR 0、C=C(R 0) 2、O、S、S=O、SO 2、NR 0、PR 0、P(=O)R 0或P(=S)R 0，較佳地E 10為C(R 0) 2； 其中R 0具有與上述相同的定義； E 11在每次出現時係相同或不同地選自C=O、O、S、S=O或SO 2，較佳為O或S，更佳為O；及 Ar 13在每次出現時相同或不同地為具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R取代。 根據一較佳實施態樣，式(E-1)之發光體包含基團Ar 10，其係選自式(Ar 10-15)至(Ar 10-22)之基團，其中d較佳等於1，及其中較佳地至少一個基團Ar 11、Ar 12係選自式(Ar 10-15)至(Ar 10-22)之基團。 根據一非常佳的實施態樣，式(E-1)之發光體係選自式(E-1-1)至(E-1-6)之發光體，
Figure 02_image117
Figure 02_image119
其中該等符號具有與上述相同的意義和其中： f     為0、1或2；及 在上述式(E-1-1)至(E-1-6)之化合物中所表示的苯環可經一或多個基團R取代在所有自由位置。 特佳地，式(E-1)化合物係選自式(E-1-1-A)至(E-1-6-A)之化合物，
Figure 02_image121
Figure 02_image123
Figure 02_image125
其中該等符號和標號具有與上述相同的意義，及其中在上述式(E-1-1-A)至(E-1-6-A)之化合物中所表示的苯環可經一或多個基團R取代在所有自由位置。 較佳地，式(E-2)之螢光發光體係選自式(E-2-1)至(E-2-43)之螢光發光體、
Figure 02_image127
Figure 02_image129
Figure 02_image131
Figure 02_image133
Figure 02_image135
Figure 02_image137
其中式(E-2-1)至(E-2-43)之基團可經一或多個基團R取代在所有自由位置；及其中E 20具有與上述相同的定義。較佳地，E 20為C(R 0) 2。 式(E-2)化合物較佳係選自式(E-2-32)至(E-2-43)之化合物。更佳地，式(E-2)化合物係選自化合物(E-2-32-A)至(E-2-43-A)：
Figure 02_image139
Figure 02_image141
Figure 02_image143
其中該等符號具有與上述相同的意義，及其中在上述式(E-2-32-A)至(E-2-43-A)之化合物中所表示的苯和萘環可經一或多個基團R取代在所有自由位置。 較佳地，式(E-3)之螢光發光體係選自式(E-3-1)之螢光發光體，
Figure 02_image145
其中該等符號和標號具有與上述相同的意義。 更佳地，式(E-3)之螢光發光體係選自式(E-3-2)之螢光發光體，
Figure 02_image147
其中該等符號E 30至E 33具有與上述相同的意義；其中t為0或1，其中當t為0時，基團E 32不存在而基團R 10存在且其置換至E 32的鍵；及其中 R 10在每次出現時相同或不同地代表H、D、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R’) 2、N(Ar) 2、NO 2、Si(R’) 3、B(OR’) 2、OSO 2R’、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基(thioalkyl)或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R’取代，其中在各情況下一或多個非相鄰的CH 2基團可經R’C=CR’、C≡C、Si(R’) 2、Ge(R’) 2、Sn(R’) 2、C=O、C=S、C=Se、P(=O)(R’)、SO、SO 2、O、S或CONR’置換及其中一或多個H原子可經D、F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R’取代)、或具有5至60個芳族環原子之芳氧基(其可經一或多個基團R’取代)之整數；其中二個相鄰的取代基R 10可一起形成脂族或芳族環系統，其可經一或多個基團R’取代；其中R’具有與上述相同的定義。 甚至更佳地，式(E-3)之螢光發光體係選自式(E-3-3)和(E-3-4)之螢光發光體，
Figure 02_image149
其中該等符號和標號具有與上述相同的意義。 較佳地，式(E-4)之螢光發光體係選自式(E-4-1)或(E-4-2)之螢光發光體，
Figure 02_image151
其中 E 41和E 42在每次出現時相同或不同地代表O、S、C(R 0) 2、C=O、C=S、C=NR 0、C=C(R 0) 2、Si(R 0) 2、BR 0、NR 0、PR 0、SO 2、SeO 2或化學鍵，其中E 41較佳為鍵； R 20在每次出現時相同或不同地代表H、D、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R’) 2、N(Ar) 2、NO 2、Si(R’) 3、B(OR’) 2、OSO 2R’、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基(thioalkyl)或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R’取代，其中在各情況下一或多個非相鄰的CH 2基團可經R’C=CR’、C≡C、Si(R’) 2、Ge(R’) 2、Sn(R’) 2、C=O、C=S、C=Se、P(=O)(R’)、SO、SO 2、O、S或CONR’置換及其中一或多個H原子可經D、F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R’取代)、或具有5至60個芳族環原子之芳氧基(其可經一或多個基團R’取代)；其中二個相鄰的取代基R 20可一起形成脂族或芳族環系統，其可經一或多個基團R’取代；其中R’具有與上述相同的定義； g    為0或1。 更佳地，式(E-4)之螢光發光體係選自式(E-4-1-A)或(E-4-2-A)之螢光發光體，
Figure 02_image153
其中該等符號具有與上述相同的意義。 根據一較佳實施態樣，式(E-1)、(E-2)、(E-3)或(E-4)之螢光發光體包含基團RS，其中基團RS係： -  選自以式(RS-a)之基團的下列通式表示之支鏈或環狀烷基，
Figure 02_image155
其中 R 22、R 23、R 24在每次出現時係相同或不同地選自H、具有1至10個碳原子之直鏈烷基、或具有3至10個碳原子之支鏈或環狀烷基，其中上述基團可各自經一或多個基團R 25取代，且其中基團R 22、R 23、R 24中之二者或所有基團R 22、R 23、R 24可連接以形成(多)環狀烷基，其可經一或多個基團R 25取代； R 25在每次出現時係相同或不同地選自具有1至10個碳原子之直鏈烷基、或具有3至10個碳原子之支鏈或環狀烷基； 其先決條件為在每次出現時，基團R 22、R 23和R 24中之至少一者不為H，其先決條件為在每次出現時，所有基團R 22、R 23和R 24一起具有至少4個碳原子且先決條件為在每次出現時，若基團R 22、R 23、R 24中之二者為H，則其餘基團不為直鏈；或 -  選自以下列通式(RS-b)表示之支鏈或環狀烷氧基
Figure 02_image157
其中 R 26、R 27、R 28在每次出現時係相同或不同地選自H、具有1至10個碳原子之直鏈烷基、或具有3至10個碳原子之支鏈或環狀烷基，其中上述基團可各自經一或多個如上定義之基團R 25取代，且其中基團R 26、R 27、R 28中之二者或所有基團R 26、R 27、R 28可連接以形成(多)環狀烷基，其可經一或多個如上定義之基團R 25取代； 其先決條件為在每次出現時，基團R 26、R 27和R 28中只有一者可為H； -  選自以下列通式(RS-c)表示之芳烷基
Figure 02_image159
其中 R 29、R 30、R 31在每次出現時係相同或不同地選自H、具有1至10個碳原子之直鏈烷基、或具有3至10個碳原子之支鏈或環狀烷基，其中上述基團可各自經一或多個基團R 32取代、或具有6至30個芳族環原子之芳族環系統，其在各情況下可經一或多個基團R 32取代，且其中基團R 29、R 30、R 31中之二者或全部可連接以形成(多)環狀烷基或芳族環系統，彼等各自可經一或多個基團R 32取代； R 32在每次出現時係相同或不同地選自具有1至10個碳原子之直鏈烷基、或具有3至10個碳原子之支鏈或環狀烷基、或具有6至24個芳族環原子之芳族環系統； 其先決條件為在每次出現時，基團R 29、R 30和R 31中之至少一者不為H，且在每次出現時，基團R 29、R 30和R 31中之至少一者為或含有具有至少6個芳族環原子之芳族環系統； -  選自以下列通式(RS-d)表示之芳環系統
Figure 02_image161
其中 R 40至R 44在每次出現時係相同或不同地選自H、具有1至10個碳原子之直鏈烷基、或具有3至10個碳原子之支鏈或環狀烷基，其中上述基團可各自經一或多個基團R 32取代、或具有6至30個芳族環原子之芳族環系統，其在各情況下可經一或多個基團R 32取代，且其中基團R 40至R 44中之二或更多者可連接以形成(多)環狀烷基或芳族環系統，彼等各自可經一或多個如上定義之基團R 32取代；或 -  選自式(RS-e)之基團，
Figure 02_image163
其中式(RS-e)中之虛線鍵表示至螢光發光體的鍵結，其中Ar 50、Ar 51在每次出現時相同或不同地代表具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R取代；及其中m為選自1至10的整數。 較佳地，式(RS-e)之基團中的標號m為選自1至6，非常較佳地選自1至4的整數。 較佳地，其中Ar 50、Ar 51在每次出現時相同或不同地代表具有5至40個(較佳5至30個，更佳6至18個)芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R取代。更佳地，Ar 50、Ar 51係選自苯基、聯苯、聯三苯(terphenyl)、聯四苯(quaterphenyl)、茀、螺二茀、萘、蒽、菲、聯伸三苯(triphenylene)、丙二烯合茀(fluoranthene)、二苯并呋喃、咔唑和二苯并噻吩，其在各情況下可經一或多個基團R取代。非常較佳地，至少一個基團Ar 50或Ar 51為茀，其可經一或多個基團R取代。 更特別地，較佳的是至少一個基團Ar 50代表式(Ar50-2)之基團及/或至少一個基團Ar 51代表式(Ar51-2)之基團，
Figure 02_image165
其中 式(Ar50-2)中之虛線鍵表示至螢光發光體和至基團Ar 50或Ar 51的鍵結；及式(Ar51-2)中之虛線鍵表示至Ar 50的鍵結； E 4係選自-C(R 0a) 2-、-Si(R 0a) 2-、-O-、-S-或-N(R 0a)-，較佳-C(R 0a) 2； R 0a在每次出現時相同或不同地代表H、D、F、CN、具有1至40個(較佳1至20個，更佳1至10個) C原子之直鏈烷基或具有3至40個(較佳3至20個，更佳3至10個) C原子之支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至60個(較佳5至40個，更佳5至30個，非常較佳5至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)；其中二個相鄰的取代基R 0a可形成單環或多環的脂族環系統或芳族環系統，其可經一或多個基團R取代，其具有與上述相同的意義；及 式(Ar50-2)和(Ar51-2)之基團可經基團R取代在各個自由位置，該基團R具有與上述相同的意義。 基團RS較佳位於其中RS替代R、R 0或R’之位置。 可使用於包含式(H1)和(H2)化合物之組成物中的螢光發光體之實例為芳族蒽胺、芳族蒽二胺、芳族芘胺、芳族芘二胺、芳族
Figure 111113012-001
胺(chrysenamine)或芳族
Figure 111113012-001
二胺。芳族蒽胺意指其中一個二芳胺基直接鍵結至蒽基(較佳在9位置)的化合物。芳族蒽二胺意指其中兩個二芳胺基直接鍵結至蒽基(較佳在9,10-位置)的化合物。芳族芘胺、芘二胺、
Figure 111113012-001
胺及
Figure 111113012-001
二胺係與其類似地定義，其中二芳胺基較佳地鍵結至芘之1-位置或1,6-位置。其他較佳發光體為橋聯三芳基胺(例如根據WO 2019/111971、WO2019/240251和WO 2020/067290)。其他較佳發光體為茚并茀胺或茚并茀二胺(例如根據WO 2006/108497或WO 2006/122630)、苯并茚并茀胺或苯并茚并茀二胺(例如根據WO 2008/006449)、及二苯并茚并茀胺或二苯并茚并茀二胺(例如根據WO 2007/140847)、和WO 2010/012328中所揭示之含有縮合芳基之茚并茀衍生物。又其他較佳發光體為如WO 2015/ 158409中所揭示之苯并蒽衍生物、如WO 2017/036573中所揭示之蒽衍生物、如WO 2016/150544中之經由雜芳基連接的茀二聚物或如WO 2017/028940和WO 2017/028941中所揭示之啡㗁𠯤衍生物。同樣較佳者為WO 2012/048780和WO 2013/185871中所揭示之芘芳基胺(pyrenarylamine)。同樣較佳者為WO 2014/037077中所揭示之苯并茚并茀胺、WO 2014/106522中所揭示之苯并茀胺和WO 2014/111269或WO 2017/036574、WO 2018/007421中所揭示之茚并茀。較佳亦為如WO 2018/095888、WO 2018/095940、WO 2019/ 076789、WO 2019/170572以及未公開申請案PCT/ EP2019/072697、PCT/EP2019/072670和PCT/EP2019/ 072662中所揭示之包含二苯并呋喃或茚并二苯并呋喃部分之發光體。同樣較佳者為如例如WO 2015/102118、CN108409769、CN107266484、WO2017195669、US2018069182中以及未公開申請案EP 19168728.4、EP 19199326.0和EP 19208643.7中所揭示之硼衍生物。 在本發明的情況下，非常適合的螢光發光體為WO 2018/007421中所揭示之茚并茀衍生物和WO 2019/076789中所揭示之二苯并呋喃衍生物。 可使用於包含式(H1)和(H2)化合物之組成物的較佳螢光發光化合物之實例係描述於下表中：
Figure 02_image167
Figure 02_image169
Figure 02_image171
Figure 02_image173
Figure 02_image175
Figure 02_image177
Figure 02_image179
Figure 02_image181
Figure 02_image183
Figure 02_image185
Figure 02_image187
Figure 02_image189
Figure 02_image191
Figure 02_image193
Figure 02_image195
Figure 02_image197
Figure 02_image199
Figure 02_image201
Figure 02_image203
Figure 02_image205
Figure 02_image207
Figure 02_image209
Figure 02_image211
Figure 02_image213
Figure 02_image215
Figure 02_image217
Figure 02_image219
Figure 02_image221
Figure 02_image223
Figure 02_image225
Figure 02_image227
Figure 02_image229
Figure 02_image231
Figure 02_image233
Figure 02_image235
Figure 02_image237
Figure 02_image239
Figure 02_image241
Figure 02_image243
Figure 02_image245
Figure 02_image247
Figure 02_image249
Figure 02_image251
Figure 02_image253
Figure 02_image255
Figure 02_image257
Figure 02_image259
根據本發明，式(H1)化合物和式(H2)化合物一起存在於組成物中，較佳存在於均勻混合物中。 較佳地，式(H1)化合物係以等於或高於組成物的1重量%的比例存在於組成物中。更佳地，式(H1)化合物係以1至99%，較佳10至95%，更佳20至90%，特佳30至85%，非常特佳40至80%的比例存在於組成物中。 較佳地，式(H2)化合物係以等於或高於組成物的1重量%的比例存在於組成物中。更佳地，式(H2)化合物係以1至99%，較佳5至90%，更佳10至80%，特佳15至70%，非常特佳20至60%的比例存在於組成物中。 根據一較佳實施態樣，根據本發明之組成物另外包含至少一種螢光發光體。在此情況下，較佳的是螢光發光體係以介於0.1和50.0%，較佳介於0.5和20.0%之間，特佳地介於1.0和10.0%之間的比例存在於組成物中。 就本申請案目的而言，以%表示的比例規格，若化合物是從氣相中施加，則意指體積%，及若化合物是從溶液施加，則意指重量%。 為了從液相處理根據本發明之化合物(例如藉由塗佈方法如旋轉塗佈或藉由印刷方法)，需要根據本發明之組成物的調配物。此等調配物可為例如溶液、分散液或乳液。為此目的，較佳可為使用二或更多種溶劑之混合物。溶劑較佳地選自有機和無機溶劑，更佳為有機溶劑。溶劑非常佳地選自烴、醇、酯、醚、酮和胺。適合且較佳的溶劑為(例如)甲苯、苯甲醚、鄰-、間-或對-二甲苯、苯甲酸甲酯、對稱三甲苯、四氫萘、藜蘆醚、THF、甲基-THF、THP、氯苯、二㗁烷、苯氧基甲苯(特別是3-苯氧基甲苯)、(-)-葑酮、1,2,3,5-四甲基苯、1,2,4,5-四甲基苯、1-甲基萘、1-乙基萘、癸基苯、苯基萘、異戊酸薄荷酯、異丁酸對甲苯基酯、己酸環己酯(cyclohexal hexanoate)、對甲基苯甲酸乙酯、鄰甲苯甲酸乙酯、間甲苯甲酸乙酯、十氫萘、2-甲氧基苯甲酸乙酯、二丁基苯胺、二環己基酮、異山梨醇二甲基醚、十氫萘、2-甲基聯苯、辛酸乙酯、辛酸辛酯、癸二酸二乙酯、3,3-二甲基聯苯、1,4-二甲基萘、2,2’-二甲基聯苯、2-甲基苯并噻唑、2-苯氧基乙醇、2-吡咯啶酮、3-甲基苯甲醚、4-甲基苯甲醚、3,4-二甲基苯甲醚、3,5-二甲基苯甲醚、苯乙酮、α-萜品醇、苯并噻唑、苯甲酸丁酯、異丙苯、環己醇、環己酮、環己基苯、十氫萘、十二烷基苯、苯甲酸乙酯、茚烷、NMP、對-異丙基甲苯、苯基乙基醚、1,4-二異丙基苯、二苯甲基醚、二乙二醇丁基甲基醚、三乙二醇丁基甲基醚、二乙二醇二丁基醚、三乙二醇二甲基醚、二乙二醇單丁基醚、三丙二醇二甲基醚、四乙二醇二甲基醚、2-異丙基萘、戊基苯、己基苯、庚基苯、辛基苯、1,1-雙(3,4-二甲基苯基)乙烷或此等溶劑之混合物。 本發明因此再者關於一種包含根據本發明之式(H1)化合物和式(H2)化合物及至少一種溶劑之調合物。溶劑可為上述溶劑中之一者或這些溶劑的混合物。 有機溶劑在根據本發明之調配物中的比例基於調配物的總重量較佳為至少60重量%，較佳為至少70重量%和更佳為至少80重量%。 根據本發明之調配物可用於製造一層或多層結構，其中依據製造較佳的電子或光電組件(例如OLED)之要求，有機功能材料可存在於該等層中。 本發明之調配物較佳可使用於在基板上或在施加至基板的多個層中之一層上形成包含根據本發明之組成物的功能層。 本發明的又另一目的為一種製造電子裝置之方法，其中至少一層係從施加本發明調配物而獲得。較佳地，將根據本發明之調配物施加於基板或另一層並接著乾燥。 得自根據本發明之調配物的功能層可例如以泛塗(flood coating)、浸塗、噴塗、旋轉塗佈、網版印刷、凸版印刷、凹版印刷、旋轉印刷、輥塗、快乾印刷(flexographic printing)、平版印刷或噴嘴印刷，較佳噴墨印刷在基板上或施加至基板之層中的一者而製得。 根據本發明之調配物施加至基板或已施加的功能層之後，可進行乾燥步驟以便移除溶劑。較佳地，乾燥步驟包含真空乾燥，其較佳接著進行層的退火。真空乾燥在此較佳可在從10 -7毫巴至1巴之範圍，特佳在從10 -6毫巴至1巴之範圍的壓力下進行。真空乾燥較佳在從10至40℃，更佳15至30℃之範圍的溫度下進行。真空乾燥步驟後較佳接著進行層的熱退火。層的熱退火較佳在從120℃至180℃，較佳從130℃至170℃，更佳140℃至160℃的溫度下進行。 因此，本發明關於一種製造電子裝置之方法，該電子裝置包含至少一層包含根據本發明之組成物的層，其中該方法包含下列步驟： a) 製備一種根據本發明之調配物； b) 將步驟a)中製備的調配物施加在基板上或另一層上以形成包含根據本發明之組成物的層； c) 將該層乾燥以移除溶劑。 較佳地，在步驟b)中，調配物係藉由從液相處理，更佳地經由塗佈方法或印刷方法，非常更佳地藉由印刷方法，特佳地藉由噴墨印刷方法而施加。 本發明的另一目標為電子裝置，其包括陽極、陰極和至少一個介於二者之間的功能層，其中此功能層包含根據本發明之組成物。較佳地，包含根據本發明之組成物的該至少一個功能層為發光層。 電子裝置較佳係選自有機電致發光裝置(OLED)、有機積體電路、有機場效電晶體、有機薄膜電晶體、有機發光電晶體、有機太陽能電池、有機染料敏化太陽能電池、有機光學檢測器、有機感光器(photoreceptor)、有機場淬滅裝置、發光電化學電池、有機雷射二極體和有機電漿子發射裝置。更佳地，電子裝置為有機電致發光裝置(OLED)。 有機電致發光裝置包含陰極、陽極和至少一個發光層，其包含根據本發明之組成物。除了這些層以外，有機電致發光裝置亦可包含其他層，例如在各情況下一或多個電洞注入層、電洞傳輸層、電洞阻擋層、電子傳輸層、電子注入層、激子阻擋層、電子阻擋層、及/或電荷產生層。同樣可能在二個發光層之間引入具有例如激子阻擋功能之中間層。然而，應指出的是此等層各者不一定必須存在。有機電致發光裝置在此可包含一個發光層或多個發光層。若存在多個發光層，則此等發光層較佳地具有總計多個在380 nm和750 nm之間的發光最大值，整體導致白色發光，亦即將能夠發螢光或磷光的各種發光化合物使用於發光層中。特佳者為具有三個發光層之系統，其中該三層呈現藍色、綠色及橙色或紅色發光(基本結構參見例如WO 2005/011013)。此等可為螢光或磷光發光層或其中螢光和磷光發光層彼此組合的混合系統。 所涉及的電子裝置可包含單一發光層，其包含根據本發明之組成物，或其可包含二更多個發光層。 根據本發明之組成物可包含一或多種其他基質材料。 較佳其他基質材料係選自下列之類別：寡聚伸芳基(oligoarylene)(例如根據EP 676461之2,2’,7,7’-四苯基螺二茀或二萘基蒽)，特別是含有縮合芳族基團之寡聚伸芳基、寡聚伸芳基伸乙烯基(oligoarylenevinylene)(例如根據EP 676461之DPVBi或螺-DPVBi)、多牙(polypodal)金屬錯合物(例如根據WO 2004/081017)、電洞傳導化合物(例如根據WO 2004/058911)、電子傳導化合物，特別是酮、氧化膦、亞碸、等等(例如根據WO 2005/084081和WO 2005/084082)、阻轉異構物(例如根據WO 2006/048268)、硼酸衍生物(例如根據WO 2006/117052)、或苯并蒽(例如根據WO 2008/145239)。特佳基質材料係選自下列之類別：包含萘、蒽、苯并蒽及/或芘或這些化合物的阻轉異構物之寡聚伸芳基、寡聚伸芳基伸乙烯基、酮、氧化膦和亞碸。非常特佳的基質材料係選自下列之類別：包含蒽、苯并蒽、苯并菲及/或芘或這些化合物的阻轉異構物之寡聚伸芳基。寡聚伸芳基就本發明的意義而言意指一種其中至少三個芳基或伸芳基彼此鍵結之化合物。 在根據本發明之有機電致發光裝置中用作為之對應的功能材料之一般較佳材料類別係表示於下。 適當電荷傳輸材料，如可使用於根據本發明之電子裝置的電洞注入或電洞傳輸層或電子阻擋層或於電子傳輸層中，為(例如) Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010中所揭示之化合物或根據先前技術使用於此等層中之其他材料。 可使用於電子傳輸層之材料為根據先前技術用作為電子傳輸層中之電子傳輸材料的所有材料。特別適合的是鋁錯合物(例如，Alq 3)、鋯錯合物(例如，Zrq 4)、鋰錯合物(例如LiQ)、苯并咪唑衍生物、三𠯤衍生物、嘧啶衍生物、吡啶衍生物、吡𠯤衍生物、喹㗁啉衍生物、喹啉衍生物、㗁二唑衍生物、芳族酮、內醯胺、硼烷、二氮磷雜環戊二烯(diazaphosphole)衍生物和氧化膦衍生物。此外，適當材料為上述化合物之衍生物，如JP 2000/053957、WO 2003/060956、WO 2004/028217、WO 2004/080975和WO 2010/072300中所揭示。 可用於根據本發明之電致發光裝置中的電洞傳輸層、電洞注入層或電子阻擋層中之較佳電洞傳輸材料為茚并茀胺衍生物(例如根據WO 06/122630或WO 06/100896)、EP 1661888中所揭示之胺衍生物、六氮雜聯伸三苯衍生物(例如根據WO 01/049806)、含有縮合芳族環之胺衍生物(例如根據US 5,061,569)、WO 95/09147中所揭示之胺衍生物、單苯并茚并茀胺(例如根據WO 08/006449)、二苯并茚并茀胺(例如根據WO 07/140847)、螺二茀胺(例如根據WO 2012/034627或WO 2013/120577)、茀胺(例如根據申請案EP 2875092、EP 2875699和EP 2875004)、螺二苯并哌喃胺(例如根據WO 2013/083216)和二氫吖啶衍生物(例如根據WO 2012/150001)。根據本發明之化合物也可用作為電洞傳輸材料。 有機電致發光裝置之陰極較佳包含具有低功函數之金屬、金屬合金或包含各種金屬之多層結構，諸如，例如鹼土金屬、鹼金屬、主族金屬或鑭系元素(例如Ca、Ba、Mg、Al、In、Mg、Yb、Sm、等等)。亦適合的是包含鹼金屬或鹼土金屬和銀之合金，例如包含鎂和銀之合金。在多層結構之情況中，除該等金屬外，也可使用具有較高功函數之其他金屬，諸如(例如)Ag或Al，在該情況中通常使用金屬之組合，諸如(例如) Ca/Ag、Mg/Ag或Ag/Ag。較佳亦可於金屬陰極與有機半導體之間引入具有高介電常數之材料的薄中間層。適合於此目的者為(例如)鹼金屬氟化物或鹼土金屬氟化物，但對應氧化物或碳酸鹽(例如LiF、Li 2O、BaF 2、MgO、NaF、CsF、Cs 2CO 3、等等)亦適合。此外，喹啉酸鋰(LiQ)可使用此目的。此層之層厚度較佳係介於0.5和5 nm之間。 陽極較佳包含具有高功函數之材料。陽極較佳具有相對於真空為大於4.5 eV之功函數。適合於此目的者一方面為具有高氧化還原電位之金屬，諸如(例如)Ag、Pt或Au。另一方面，金屬/金屬氧化物電極(例如Al/Ni/NiO x、Al/PtO x)亦可為較佳的。就一些應用而言，電極中之至少一者必須是透明或部分透明的，以便促進有機材料之照射(有機太陽能電池)或光之偶合輸出(coupling-out) (OLED、O-雷射)。較佳陽極材料在此為導電性混合金屬氧化物。特佳者為氧化銦錫(ITO)或氧化銦鋅(IZO)。此外較佳者為導電性摻雜型有機材料，特別是導電性摻雜型聚合物。 將裝置適當地(視應用而定)結構化，配備接點且最後密封，因為根據本發明之裝置的壽命在水及/或空氣存在下被縮短。 在一較佳實施態樣中，根據本發明之有機電致發光裝置特徵在於一或多層係利用昇華方法塗佈，其中該等材料係於真空昇華單元中在低於10 ‑5毫巴，較佳低於10 ‑6毫巴之初壓力下藉由氣相沈積施加。然而，初壓力在此也可能甚至更低，例如低於10 ‑7毫巴。 同樣較佳者為一種有機電致發光裝置，其特徵在於利用OVPD (有機氣相沈積)方法或輔以載體-氣體昇華法塗佈一或多層，其中該等材料係在介於10 -5毫巴和1巴之間的壓力下施加。此方法的一特殊例子為OVJP (有機氣相噴墨印刷)方法，其中該等材料係透過噴嘴直接施加且因此結構化(例如，M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301)。 此外較佳者為一種有機電致發光裝置，其特徵在於一或多層係諸如(例如)以旋轉塗佈或利用任何所欲印刷方法(諸如，例如網版印刷、快乾印刷、噴嘴印刷或平版印刷，但特佳為LITI (光誘導熱成像、熱轉移印刷)或噴墨印刷)從溶液製造。為此目的需要可溶性式(I)化合物。高溶解度可透過該等化合物之適當取代而達成。 亦可能為混合方法，其中，例如，一或多層係從溶液施加而一或多個其他層係藉由氣相沈積施加。因此，例如，可能從溶液施加發光層而可能藉由氣相沈積施加電子傳輸層。 此等方法通常為熟習此項技術者已知，且可由熟習此項技術者在無創造性的情況下應用於包含根據本發明之化合物的有機電致發光裝置。 根據本發明，包含一或多種根據本發明之化合物的電子裝置可使用於顯示器、於照明應用中用作為光源、及於醫學及/或美容應用(例如光療法)中用作為光源。 現將以下列實施例更詳細地解釋本發明，而不希望因此限制本發明。 The present invention is therefore based on the technical aim of providing compositions comprising OLED materials suitable for use in electronic devices such as OLEDs, more particularly as matrix components for fluorescent emitters. The invention is also based on the technical aim of providing compositions comprising OLED materials which are particularly suitable for use in solution processing. The invention is also based on the technical aim of providing a method. In research on novel compositions for electronic devices, it has now been found that compositions comprising compounds of formula (H1) and compounds of formula (H2) as defined below are very suitable for use in electronic devices. In particular, they can achieve one or more of the above technical objectives, preferably all of them. The present application therefore relates to a composition comprising: a first host material of formula (H1),
Figure 02_image001
The second host material of formula (H2),
Figure 02_image003
and dopant materials; wherein the following applies to the symbols and designations used: G is an aromatic or heteroaromatic ring system having 6 to 60 aromatic ring atoms, which in each case may also be via one or more A group R X is substituted; G 2 is a group selected from formula (G2):
Figure 02_image005
Wherein the group E is a divalent bridge selected from the following; -Y=Y-, -C(R B0 ) 2 -, Si(R B0 ) 2 -, -O-, -S-, -C(=O) -, -S(=O)-, -SO 2 -, -BR B0 -, -N(R B0 )- or -P(R B0 )-, preferably -Y=Y-, -C(R B0 ) 2 -, -O-, -S-; and wherein R B0 at each occurrence identically or differently represents H, F, CN, straight-chain alkyl having 1 to 40 C atoms or having 3 to 40 Branched or cyclic alkyl groups of C atoms (each of which may be substituted by one or more radicals R), aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms (which in each case Can be replaced by one or more groups R); wherein two adjacent substituents R B0 can form a monocyclic or polycyclic aliphatic ring system or aromatic ring system, which can be replaced by one or more groups R Substitution; Y represents CRY or N identically or differently in each occurrence; the prerequisite is that when Y is bonded to the group Ant 2 , Y represents C; Ant 1 is a group of formula (A1):
Figure 02_image007
Wherein the dotted line bond among the formula (A1) represents to the bonding position of group G 1 , and wherein group Ant 1 can be bonded to any free position of G 1 ; Ant 2 is the group of formula (A2):
Figure 02_image009
Wherein the dotted line bond in the formula (A2) represents the bonding position to the group G 2 , and wherein the group Ant 2 can be bonded to any free position of G 2 ; Ar A1 , Ar B1 , Ar AS , Ar BS in each Identical or different occurrences of an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R A1 to R A8 , R B1 to R B8 , RY , R X identically or differently represent at each occurrence a group selected from the group consisting of: H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar , P(=O)(Ar) 2 , S(=O)Ar, S(=O) 2 Ar, N(R) 2 , N(Ar) 2 , NO 2 , Si(R) 3 , B(OR ) 2 , OSO 2 R, straight-chain alkyl, alkoxy or thioalkyl having 1 to 40 C atoms or branched or cyclic alkyl and alkoxy having 3 to 40 C atoms or alkylthio groups (each of which may be substituted by one or more groups R, where in each case one or more non-adjacent CH2 groups may be substituted by RC=CR, C≡C, Si(R) 2. Ge(R) 2 , Sn(R) 2 , C=O, C=S, C=Se, P(=O)(R), SO, SO 2 , O, S or CONR replacement and one or Multiple H atoms may be replaced by D, F, Cl, Br, I, CN or NO), aromatic or heteroaromatic ring systems with 5 to 60 aromatic ring atoms (which in each case may be replaced by a or more groups R substituted), and aryloxy groups having 5 to 60 aromatic ring atoms (which may be substituted by one or more groups R); the prerequisites are that R B1 to R B8 and RY are not represents D; and wherein two adjacent groups R A1 to R A8 , R B1 to R B8 , RY or R X can together form an aliphatic, aromatic or heteroaromatic ring system, which can be passed through one or more substituted by a group R; R at each occurrence identically or differently represents H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar) 2 , S(=O)Ar, S(=O) 2 Ar, N(R') 2 , N(Ar) 2 , NO 2 , Si(R') 3 , B(OR') 2 , OSO 2 R', Straight-chain alkyl, alkoxy or alkylthio having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 40 C atoms (each of which can be One or more groups R' are substituted, wherein in each case one or more non-adjacent CH 2 groups can be replaced by R'C=CR', C≡C, Si(R') 2 , Ge(R ') 2 , Sn(R') 2 , C=O, C=S, C=Se, P(=O)(R'), SO, SO 2 , O, S or CONR' substitution and one or more of them H atoms may be replaced by D, F, Cl, Br, I, CN or NO), aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms (which in each case may be replaced by one or a plurality of groups R'substituted), or an aryloxy group having 5 to 60 aromatic ring atoms (which may be substituted by one or more groups R'); where two adjacent substituents R may form together aliphatic or aromatic ring system, which may be substituted by one or more radicals R'; Ar is, at each occurrence, identical or different, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms , which in each case may also be substituted by one or more radicals R';R' at each occurrence identically or differently represents H, D, F, Cl, Br, I, CN, with 1 to 20 C-atom straight-chain alkyl, alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 20 C atoms (wherein each case one or more Non-adjacent CH2 groups can be replaced by SO, SO2 , O, S and one or more H atoms can be replaced by D, F, Cl, Br or I), or have 5 to 24 aromatic rings Atoms of aromatic or heteroaromatic ring systems; and n at each occurrence, identically or differently, 0 or 1; wherein when n is 0, corresponding to the absence of Ar AS or Ar BS , and an anthracenyl direct bond bound to a group G1 or G2 ; m is 0 or 1; characterized in that the compound of formula (H1) contains at least one deuterium atom, and the compound of formula (H2) is substantially free of deuterium atoms. More preferably, the compound of formula (H2) does not contain deuterium atoms. Accordingly, the radicals R and R' in the compound of formula (H2) do not represent a deuterium atom. A deuterium atom is also referred to herein as "D". Furthermore, the following definitions of chemical groups apply for the purposes of this application: Aryl in the sense of the present invention contains 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 40 aromatic ring atoms 20 aromatic ring atoms; heteroaryl in the sense of the present invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, wherein At least one is a heteroatom. Heteroatoms are preferably selected from N, O and S. This represents the basic definition. If other preferences are indicated in the description of the invention, eg with regard to the number of aromatic ring atoms or heteroatoms present, these apply. Aryl or heteroaryl here means a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine or thiophene, or a condensed (annellated) aromatic or heteroaromatic polycyclic ring, For example naphthalene, phenanthrene, quinoline or carbazole. Condensed (fused) aromatic or heteroaromatic polycyclic rings in the sense of the present application consist of two or more simple aromatic or heteroaromatic rings condensed with one another. Aryl or heteroaryl which may in each case be substituted by the groups mentioned above and which may be attached via any desired position to an aromatic or heteroaromatic ring system means in particular radicals derived from: benzene, naphthalene, anthracene, phenanthrene , pyrene, dihydropyrene,
Figure 111113012-001
(chrysene), perylene, fluoranthene, benzanthracene, triphenylene, condensed tetraphenyl, condensed pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran , thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6 -Quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenanthium, phenanthyl, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole , phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthracene Anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, thiazole, benzothraxazole, pyrimidine, benzopyrimidine, quinine phenoline, pyridine, phenanthroline, phenidine, azacarbazole, benzocarboline, morpholine, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2 ,3-Oxadiazole, 1,2,4-Oxadiazole, 1,2,5-Oxadiazole, 1,3,4-Oxadiazole, 1,2,3-Thiadiazole, 1,2 ,4-Thiadiazole, 1,2,5-Thiadiazole, 1,3,4-Thiadiazole, 1,3,5-Trisadiazole, 1,2,4-Trisadiazole, 1,2,3 -Trizole, tetrazole, 1,2,4,5-tetrazole, 1,2,3,4-tetrazole, 1,2,3,5-tetrazole, purine, pteridine, ind
Figure 111113012-002
and benzothiadiazoles. Aryloxy as defined according to the invention means an aryl group as defined above bonded via an oxygen atom. Similar definitions apply to heteroaryloxy. Aromatic ring systems in the sense of the present invention contain 6 to 60 C atoms, preferably 6 to 40 C atoms, more preferably 6 to 20 C atoms in the ring system. Heteroaromatic ring systems in the sense of the present invention contain 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is heteroatoms. Heteroatoms are preferably selected from N, O and/or S. Aromatic or heteroaromatic ring systems in the sense of the present invention are meant not necessarily to contain only aryl or heteroaryl groups, but in which additionally a plurality of aryl or heteroaryl groups can be formed by means of non-aromatic units (preferably Systems that are less than 10% atoms other than H) (such as, for example, sp 3 -mixed C, Si, N or O atoms, sp 2 -mixed C or N atoms, or sp-mixed C atoms). Thus, for example, systems such as 9,9'-spirobistilbene, 9,9'-diarylstilbene, triarylamine, diaryl ether, stilbene, etc. are also intended to be in the sense of the present invention An aromatic ring system such as a system in which two or more aryl groups are linked, for example, via a linear or cyclic alkyl, alkenyl or alkynyl group or via a silicon group. Furthermore, systems in which two or more aryl or heteroaryl groups are linked to one another via single bonds are also aromatic or heteroaromatic ring systems within the meaning of the present invention, such as, for example, systems such as biphenyl, biphenyl Benzene or diphenyltriphenyl. Aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms which may in each case also be substituted by radicals as defined above and which may be attached to the aromatic or heteroaromatic group via any desired position In particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene,
Figure 111113012-001
(chrysene), perylene, fluoranthene, condensed tetraphenyl, condensed pentaphenyl, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene , bitetraphenyl (quaterphenyl), fennel, spirodifenole, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, truxene, isotruxene, Spiroindene, spiroisotriindene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindene Indole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline , benzo-7,8-quinoline, phenanthrimidazole, phenanthrimidazole, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole ), pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole , Isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, thiazole, benzopyrimidine, pyrimidine, benzopyrimidine, quinzoline, 1,5-diazaanthracene, 2, 7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10 -Tetraazaperylene, pyridine, phenanthroline, phenanthene, morphine, fluorubin, fenidine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-tri Azole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3, 4-thiadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3, 5-three 𠯤, 1,2,4-three 𠯤, 1,2,3-three 𠯤, tetrazole, 1,2,4,5-tetra 𠯤, 1,2,3,4-tetra 𠯤, 1, 2,3,5-Tetramethalone, Purine, Pteridine, Ind
Figure 111113012-002
and benzothiadiazole, or a combination of these groups. For the purposes of the present invention, straight-chain alkyl having 1 to 40 C atoms or branched or cyclic alkyl having 3 to 40 C atoms or alkenyl or alkynyl having 2 to 40 C atoms , wherein, in addition, individual H atoms or CH groups may be substituted by groups under the definition of these groups above, preferably meaning the groups methyl, ethyl, n-propyl, isopropyl, n-butyl Base, isobutyl, secondary butyl, tertiary butyl, 2-methylbutyl, n-pentyl, secondary pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n- Heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butene Base, Pentenyl, Cyclopentenyl, Hexenyl, Cyclohexenyl, Heptenyl, Cycloheptenyl, Octenyl, Cyclooctenyl, Ethynyl, Proynyl, Butynyl, Pentyl Alkynyl, hexynyl or octynyl. Alkoxy or alkylthio having 1 to 40 C atoms preferably means methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy radical, secondary butoxy, tertiary butoxy, n-pentyloxy, secondary pentyloxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy Base, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio , isopropylthio, n-butylthio, isobutylthio, secondary butylthio, tertiary butylthio, n-pentylthio, secondary pentylthio, n-hexylthio, cyclohexylthio, n-heptyl Thio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, Vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio , cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. For the purposes of this application, the rule that two or more groups can form a ring with each other means in particular that two groups are bonded to each other with a chemical bond. This is illustrated in the following diagrams:
Figure 02_image011
In addition, however, the above rule also means that in the case where one of the two groups represents hydrogen, the second group is bonded at the position to which the hydrogen atom is bonded, and forms a ring. This is illustrated in the following diagrams:
Figure 02_image013
When two groups form a ring with each other, it is preferable that the two groups are adjacent groups. Adjacent radicals in the sense of the present invention are radicals which are bonded to atoms which are directly bonded to one another or to the same atom. According to a preferred embodiment, the molecular weight (Mw) of the compound of formula (H1) is Mw≥350 g/mol, preferably Mw≥380 g/mol, more preferably Mw≥400 g/mol, even more preferably Mw≥450 g/mol. Furthermore, it is preferred that the group G is a group selected from one of the following formulae:
Figure 02_image015
Figure 02_image017
wherein: X represents CR X or N identically or differently at each occurrence; the prerequisite is that when X is bonded to the group Ant 1 , X represents C; E 1 , E 2 , E 3 , E 4 in each The same or different occurrences represent a single bond, -BR 0 -, -C(R 0 ) 2 -, -Si(R 0 ) 2 -, -C(=O)-, -O-, -S-, -S(=O)-, -SO 2 -, -N(R 0 )- or -P(R 0 )-; with the prerequisite that only one of the radicals E 1 and E 3 may be a single bond, and Only one of the groups E 4 and E 2 may be a single bond; E 5 represents -BR 0 -, -C(R 0 ) 2 -, -Si(R 0 ) 2 -, -C(=O)-, -O-, -S-, -S(=O)-, -SO 2 -, -N(R 0 )- or -P(R 0 )-, preferably representing -C(R 0 ) 2 -, - O- or -S-, more preferably represents -O- or -S-; R 0 represents H, D, F, CN identically or differently at each occurrence, with 1 to 40 (preferably 1 to 20 1, more preferably 1 to 10) C-atom straight-chain alkyl or branched or cyclic alkyl having 3-40 (preferably 3-20, more preferably 3-10) C-atoms (each of which may be substituted by one or more groups R), having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, even more preferably 6 to 18) aromatic rings Aromatic or heteroaromatic ring system of atoms (which in each case may be substituted by one or more groups R); where two adjacent substituents R can form a monocyclic or polycyclic aliphatic ring system or an aromatic ring system, which may be substituted by one or more groups R; R X , R have the same definitions as above. Preferably, E 1 , E 2 , E 3 , E 4 represent identically or differently at each occurrence a single bond, -O- or -S-; a prerequisite for this is that one of the groups E 1 and E 3 One is a single bond and the other is -O- or -S-, and one of the groups E4 and E2 is a single bond and the other is -O- or -S-. More preferably, E 1 and E 2 represent -O- or -S- and E 3 and E 4 represent single bonds. Among the structures of formulas (G1-1) to (G1-12), the following structures are preferred: (G1-1), (G1-3), (G1-4), (G1-5), (G1-7 ), (G1-9), (G1-10), (G1-11) and (G1-12). The following structures are particularly preferred: (G1-1), (G1-3), (G1-4), (G1-5,) (G1-9), (G1-10). Preferably, the compound of formula (H1) is selected from compounds of the following formulae:
Figure 02_image019
Figure 02_image021
Figure 02_image023
Figure 02_image025
wherein the symbols have the same meanings as above and wherein the compounds of formulas (G1-1-1) to (G1-12-3) contain at least one deuterium atom. The host material (H1) is preferably selected from the formulas (G1-1-1), (G1-2-1), (G1-3-1), (G1-4-1), (G1-4-2) , (G1-5-1), (G1-6-1), (G1-7-1), (G1-8-1), (G1-9-1), (G1-9-3), ( Compounds of G1-10-1), (G1-10-3), (G1-11-1), (G1-11-3), (G1-12-1), (G1-12-3). The host material (H1) is very preferably selected from the formulas (G1-1-1), (G1-3-1), (G1-4-1), (G1-4-2), (G1-5-1) , (G1-7-1) (G1-9-1), (G1-10-1), (G1-11-1) and (G1-12-1) compounds. According to a preferred embodiment, the index m in the formula (H1) is equal to 0, and the first host compound of the formula (H1) contains only one group Ant 1 . The bonding positions on groups (G1-1) to (G1-10) can be numbered as follows:
Figure 02_image027
Figure 02_image029
Figure 02_image031
Figure 02_image033
Figure 02_image035
Figure 02_image037
Examples of suitable bonding positions for the group Ant 1 are shown in the table below:
Figure 02_image039
Figure 02_image041
The symbol "-" indicates that there is no second group Ant 1 . Among formulas (G1-1-1) to (G1-12-6), compounds (G1-1-1), (G1-1-2), (G1-1-4), (G1-2-3 ), (G1-2-4), (G1-2-7), (G1-3-1), (G1-3-3), (G1-4-2), (G1-4-3), (G1-4-4), (G1-4-12), (G1-4-13), (G1-5-2), (G1-5-3), (G1-5-4), (G1 -5-14), (G1-5-12), (G1-5-17), (G1-6-1), (G1-7-1), (G1-7-2), (G1-7 -3), (G1-7-5), (G1-8-1), (G1-8-2), (G1-8-3), (G1-8-7), (G1-8-9 ), (G1-9-1), (G1-9-3), (G1-9-5), (G1-10-1), (G1-10-3), (G1-10-7), (G1-11-2), (G1-11-6), (G1-11-5), (G1-12-1) are preferred, wherein the second group Ant 1 does not exist in the compound (G1-4 -12) is better. The following groups are very preferred: (G1-1-1), (G1-1-2), (G1-2-3), (G1-2-4), (G1-3-1), (G1 -4-2), (G1-4-3), (G1-4-4), (G1-5-2), (G1-5-3), (G1-5-4), (G1-7 -1), (G1-7-2), (G1-8-1), (G1-8-2), (G1-8-3), (G1-9-1), (G1-10-1 ), (G1-12-1). Preferably, the groups Ar A1 and Ar B1 are identical or different at each occurrence selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, Fluorine, spirodipic, naphthalene, anthracene, phenanthrene, triphenylene, allene combined fluoranthene, condensed tetraphenyl,
Figure 111113012-001
(chrysene), benzanthracene, triphenylene, pyrene or perylene, dibenzofuran, carbazole and dibenzothiophene, each of which may be substituted at any free position by one or more groups R; and wherein Ar A1 and Ar B1 can also be a combination of two or more of the above groups. More preferably, the groups Ar A1 and Ar B1 are identical or different at each occurrence selected from the group consisting of: phenyl, biphenyl, terphenyl, tetraphenyl, naphthalene, phenanthrene, which Each may be substituted by one or more groups R at any free position. Preferably, the group Ant 1 is a group of one of the formulas (A1-1) to (A1-5):
Figure 02_image043
Figure 02_image045
Figure 02_image047
Figure 02_image049
Figure 02_image051
wherein the dotted line bond in formula (A1-1) to (A1-5) represents the bonding position to group G 1 , wherein group Ant 1 can be bonded to any free position of G 1 ; and wherein R A9 to R A21 represents, identically or differently at each occurrence, a group selected from the group consisting of H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)( Ar ) , S(=O)Ar, S(=O) 2 Ar, N(R) 2 , N(Ar) 2 , NO 2 , Si(R) 3 , B(OR) 2 , OSO 2 R, with 1 to Straight-chain alkyl, alkoxy or alkylthio (thioalkyl) having 40 C atoms or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 40 C atoms (they can each be passed through One or more groups R are substituted, wherein in each case one or more non-adjacent CH 2 groups can be substituted via RC=CR, C≡C, Si(R) 2 , Ge(R) 2 , Sn( R) 2 , C=O, C=S, C=Se, P(=O)(R), SO, SO 2 , O, S or CONR replacement and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 ), an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (which in each case may be substituted by one or more groups R), and Aryloxy groups having 5 to 60 aromatic ring atoms (which may be substituted by one or more groups R); wherein two adjacent groups R A9 to R A21 may together form an aliphatic, aromatic or hetero Aromatic ring systems which may be substituted by one or more groups R. Preferably, R A1 to R A8 represent H, D, F, linear chains with 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms identically or differently at each occurrence Alkyl, alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or alkylthio with 3 to 40 (preferably 3 to 20, more preferably 3 to 10) C atoms ( Each of them may be substituted by one or more groups R, wherein in each case one or more non-adjacent CH2 groups may be replaced by RC=CR, C≡C, O or S and one or more of them Aromatic or heteroaromatic rings having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18) aromatic ring atoms, each H atom may be replaced by D or F) system (which in each case may be substituted by one or more radicals R). More preferably, R A1 to R A8 represent H, D, F, straight chain with 1 to 20 (preferably 1 to 10, more preferably 1 to 6) C atoms identically or differently at each occurrence Alkyl or branched or cyclic alkyl having 3 to 20 (preferably 3 to 10, more preferably 3 to 6) C atoms (each of which may be substituted by one or more groups R), having Aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) of 5 to 40 (preferably 5 to 30, more preferably 5 to 18) aromatic ring atoms. Particularly preferably, R A1 to R A8 are selected from H and D. Preferably, R A9 to R A21 represent H, D, F, straight chain with 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms identically or differently at each occurrence Alkyl, alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or alkylthio with 3 to 40 (preferably 3 to 20, more preferably 3 to 10) C atoms ( Each of them may be substituted by one or more groups R, wherein in each case one or more non-adjacent CH2 groups may be replaced by RC=CR, C≡C, O or S and one or more of them Aromatic or heteroaromatic rings having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18) aromatic ring atoms, each H atom may be replaced by D or F) system (which in each case may be substituted by one or more radicals R). More preferably, R A9 to R A21 represent H, D, F, straight chain with 1 to 20 (preferably 1 to 10, more preferably 1 to 6) C atoms identically or differently at each occurrence Alkyl or branched or cyclic alkyl having 3 to 20 (preferably 3 to 10, more preferably 3 to 6) C atoms (each of which may be substituted by one or more groups R), having Aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) of 5 to 40 (preferably 5 to 30, more preferably 5 to 18) aromatic ring atoms. Particularly preferably, R A9 to R A21 are selected from H and D. More preferably, the group Ant 1 is a group of one of the formulas (A1-1-D) to (A1-5-D):
Figure 02_image053
Figure 02_image055
Figure 02_image057
Wherein x is an integer selected from 0 to 8 (more preferably from 1 to 8); y1 is an integer selected from 0 to 5 (more preferably from 1 to 5); y2 is an integer selected from 0 to 4 (more preferably an integer from 1 to 4); y3 is an integer selected from 0 to 3 (more preferably from 1 to 3); z is an integer selected from 0 to 7 (more preferably from 1 to 7). For example, if the label x represents 8, the anthracene group in formula (A1-1-D) contains 8 deuterated atoms, which means that the anthracene group in formula (A1-1-D) is completely deuterated. As mentioned above, the compound of formula (H1) contains at least one deuterium atom. At least one deuterium atom may be a substituent on the group Ant 1 or G 1 . According to a preferred embodiment, the at least one deuterium atom is a substituent on the group Ant 1 . When the at least one deuterium atom is a substituent on the group Ant 1 , it is preferred: - in formula (A1): at least one group R A1 to R A8 represents at least one of the deuterium atom or the group Ar A1 The group R represents a deuterium atom; - in the formulas (A1-1) to (A1-5): at least one group R A1 to R A8 represents a deuterium atom or at least one group R A9 to R A21 represents a deuterium atom; - In formulas (A1-1-D) to (A1-5-D): at least one index selected from x, y1, y2, y3 and z present in the formulas is not equal to 0. According to a preferred embodiment, the at least one deuterium atom is a substituent on the group G 1 . In this case it is preferred that at least one group R X represents a deuterium atom. More particularly, it is preferred that at least 10% of the substituents R x present in the group G 1 represent deuterium atoms. More preferably, at least 20% of the substituents R x present in the group G represent deuterium atoms, or at least 30% of the substituents R x present in the group G represent deuterium atoms, or at least 40% of the The substituents R x present in the group G represent deuterium atoms, or at least 50% of the substituents R x present in the group G represent deuterium atoms, or at least 60% of the substituents present in the group G the substituent R x represents a deuterium atom, or at least 70% of the substituents R x present in the group G represent a deuterium atom, or at least 80% of the substituents R x present in the group G represent a deuterium atom, Or at least 90% of the substituents R x present in the group G represent deuterium atoms. Preferably, R X represents H, D, F, straight-chain alkyl having 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms identically or differently at each occurrence, Alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 40 (preferably 3 to 20, more preferably 3 to 10) C atoms (their respective Can be substituted by one or more groups R, where in each case one or more non-adjacent CH groups can be replaced by RC=CR, C≡C, O or S and where one or more H atoms Aromatic or heteroaromatic ring systems (which may be replaced by D or F), having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, especially preferably 5 to 18) aromatic ring atoms (the may in each case be substituted by one or more radicals R). More preferably, R X represents H, D, F, linear alkyl having 1 to 20 (preferably 1 to 10, more preferably 1 to 6) C atoms or A branched or cyclic alkyl group having 3 to 20 (preferably 3 to 10, more preferably 3 to 6) C atoms (each of which may be substituted by one or more groups R), having 5 to 40 Aromatic or heteroaromatic ring systems (preferably 5 to 30, more preferably 5 to 18) aromatic ring atoms (which in each case may be substituted by one or more radicals R). More preferably, RX is selected from H and D. It is particularly preferred that the compound of formula (H1) is at least 10% deuterated with a deuterium atom which is a substituent on the group G1 , on the group Ant1 or on both the groups G1 and Ant1 . This means that at least 10% of the available hydrogen atoms in the compound of formula (H1) are replaced by deuterium atoms. More preferably, the compound of formula (H1) is at least 20% deuterated, or at least 30% deuterated, or at least 40% deuterated, or at least 50% deuterated, or at least 60% deuterated, or at least 70% deuterated , or at least 80% deuterated, or at least 90% deuterated. Examples of very preferred compounds of formula (H1) are shown in the table below:
Figure 02_image059
Figure 02_image061
Figure 02_image063
Figure 02_image065
Figure 02_image067
Figure 02_image069
In the structure, for example, the term "D8" or "D4" means that the corresponding ring is substituted by 8, 4 deuterium atoms, respectively. Preferably, the group G2 is a group selected from one of the following formulae:
Figure 02_image071
wherein: Y at each occurrence, identically or differently, represents CR Y or N; with the precondition that Y represents C when Y is bonded to the group Ant 2 ; and wherein the symbols RY have the same meaning as above ; and R B0 have the same meaning as above. Preferably, R B0 represents H identically or differently at each occurrence, a straight-chain alkyl having 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms or having 3 to 40 (preferably 3 to 20, more preferably 3 to 10) branched or cyclic alkyl groups of C atoms (each of which may be substituted by one or more groups R), having 5 to 40 (more preferably 5 to 20, more preferably 6 to 18) aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more groups R) of aromatic ring atoms; wherein two adjacent The substituent R BO may form a monocyclic or polycyclic aliphatic or aromatic ring system, which may be substituted by one or more radicals R. Among the groups (G2-1) to (G2-5), the groups (G2-1) and (G2-2) are preferable. Preferably, the compound of formula (H2) is a group selected from the following formulae:
Figure 02_image073
Figure 02_image075
Wherein these symbols have the same definitions as above. Among the compounds of formula (G2-1-1) to (G2-5-2), the following compounds are preferred: (G2-1-1), (G2-2-1), (G2-4-1), (G2-5-1), (G2-5-2), more preferably (G2-1-1), (G2-2-1), (G2-5-1), (G2-5-2) , and very preferably (G2-1-1), (G2-2-1). The bonding positions of groups (G2-1) to (G2-5) can be numbered as follows:
Figure 02_image077
Figure 02_image079
Figure 02_image081
The preferred bonding position of the group Ant 2 is indicated in the table below:
Figure 02_image083
Figure 02_image085
Among the compounds of formula (G2-1-1) to (G2-5-20), the following compounds are preferred: (G2-1-6), (G2-1-7), (G2-1-9), (G2-1-10), (G2-1-11), (G2-1-12), (G2-2-7), (G2-2-8), (G2-2-9), (G2 -2-10), (G2-3-7), (G2-3-8), (G2-3-9), (G2-4-5), (G2-4-7), (G2-5 -5), (G2-5-7), (G2-5-15), (G2-5-17) and (G2-5-20). Compounds of the following formula are even better: (G2-1-6), (G2-1-9), (G2-2-8), (G2-2-9), (G2-4-7), ( G2-5-7), (G2-5-15) and (G2-5-20). Preferably, RY represents H, F, linear alkyl having 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms, alkoxy, identically or differently at each occurrence group or alkylthio group or branched or cyclic alkyl, alkoxy or alkylthio group having 3 to 40 (preferably 3 to 20, more preferably 3 to 10) C atoms (each of which can be One or more radicals R are substituted, wherein in each case one or more non-adjacent CH groups may be replaced by RC=CR, C≡C, O or S and wherein one or more H atoms may be replaced by D or F substitution), an aromatic or heteroaromatic ring system having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, especially preferably 5 to 18) aromatic ring atoms, which is in each The case may be substituted by one or more groups R. More preferably, RY represents H, F, straight-chain alkyl having 1 to 20 (preferably 1 to 10, more preferably 1 to 6) C atoms or having 3 Branched or cyclic alkyl groups with up to 20 (preferably 3 to 10, more preferably 3 to 6) C atoms (each of which may be substituted by one or more groups R), having 5 to 40 ( Aromatic or heteroaromatic ring systems of preferably 5 to 30, more preferably 5 to 18) aromatic ring atoms, which may in each case be substituted by one or more radicals R. More preferably, R Y represents H. The group Ant 2 is preferably a group of one of the formulas (A2-1) to (A2-5):
Figure 02_image087
Figure 02_image089
Figure 02_image091
Figure 02_image093
Figure 02_image095
wherein the dotted line bond in the formula (A2-1) to (A2-5) represents the bonding position to the group G 2 , and wherein the group Ant 2 can be bonded to any free position of G 2 ; and wherein R B9 to R B21 represents identically or differently at each occurrence a group selected from the group consisting of H, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar) 2 , S(=O)Ar, S(=O) 2 Ar, N(R) 2 , N(Ar) 2 , NO 2 , Si(R) 3 , B(OR) 2 , OSO 2 R, with 1 to 40 A straight-chain alkyl group, alkoxy group or alkylthio group (thioalkyl) having 3 to 40 C atoms or a branched or cyclic alkyl group, alkoxy group or alkylthio group having 3 to 40 C atoms (each of which can be passed through a or multiple groups R, where in each case one or more non-adjacent CH 2 groups can be substituted by RC=CR, C≡C, Si(R) 2 , Ge(R) 2 , Sn(R ) 2 , C=O, C=S, C=Se, P(=O)(R), SO, SO 2 , O, S or CONR replacement and one or more H atoms can be replaced by F, Cl, Br , I, CN or NO 2 replacement), an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (which in each case may be substituted by one or more groups R), and having 5 to 60 An integer of 60 aromatic ring atoms of aryloxy (which may be substituted by one or more groups R); wherein two adjacent groups of R B9 to R B21 may together form an aliphatic, aromatic or Heteroaromatic ring systems which may be substituted by one or more groups R. Preferably, R B1 to R B8 represent H, F, linear alkyl having 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms identically or differently at each occurrence , alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 40 (preferably 3 to 20, more preferably 3 to 10) C atoms (they Each may be substituted by one or more groups R), aromatic or heteroaromatic having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, especially preferably 5 to 18) aromatic ring atoms Acyclic ring systems (which in each case may be substituted by one or more radicals R). More preferably, R B1 to R B8 represent H, F, straight-chain alkyl having 1 to 20 (preferably 1 to 10, more preferably 1 to 6) C atoms identically or differently at each occurrence Or a branched or cyclic alkyl group having 3 to 20 (preferably 3 to 10, more preferably 3 to 6) C atoms (each of which may be substituted by one or more groups R), having 5 to Aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) of 40 (preferably 5 to 30, more preferably 5 to 18) aromatic ring atoms. Particularly preferably, R B1 to R B8 represent H. Preferably, R B9 to RB21 represent H, F, linear alkyl having 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms identically or differently at each occurrence , alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 40 (preferably 3 to 20, more preferably 3 to 10) C atoms (they Each may be substituted by one or more groups R), aromatic or heteroaromatic having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, especially preferably 5 to 18) aromatic ring atoms Acyclic ring systems (which in each case may be substituted by one or more radicals R). More preferably, R B9 to RB21 represent H, F, linear alkyl having 1 to 20 (preferably 1 to 10, more preferably 1 to 6) C atoms identically or differently at each occurrence Or a branched or cyclic alkyl group having 3 to 20 (preferably 3 to 10, more preferably 3 to 6) C atoms (each of which may be substituted by one or more groups R), having 5 to Aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) of 40 (preferably 5 to 30, more preferably 5 to 18) aromatic ring atoms. Examples of very preferred compounds of formula (H2) are shown in the table below:
Figure 02_image097
Figure 02_image099
Figure 02_image101
Preferably, the radicals AR AS and AR BS represent, identically or differently at each occurrence, phenyl, biphenyl, stilbene, spirobistilbene, naphthalene, phenanthrene, anthracene, dibenzofuran, dibenzothiophene, carba Azole, pyridine, pyrimidine, pyridine, pyridine, triazine, benzopyridine, benzopyridine, benzopyrimidine and quinazoline, each of which may be substituted with one or more groups R. More preferably, the radicals AR AS and AR BS represent identically or differently at each occurrence phenyl, biphenyl or naphthalene, each of which may be substituted by one or more radicals R. Preferably, R represents H, D, F, CN, N(Ar) 2 identically or differently at each occurrence, with 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C Atomic linear alkyl, alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or having 3 to 40 (preferably 3 to 20, more preferably 3 to 10) C atoms Alkylthio groups (each of which may be substituted by one or more groups R', wherein in each case one or more non-adjacent CH2 groups may be substituted by R'C=CR', C≡C, O or S replacement and wherein one or more H atoms can be replaced by D or F), or have 5 to 60 (preferably 5 to 40, more preferably 5 to 30, especially preferably 6 to 18) aromatic rings Aromatic or heteroaromatic ring systems of atoms (which in each case may be substituted by one or more radicals R'). Preferably, Ar is, at each occurrence, identical or different, aromatic having 5 to 40 (preferably 5 to 30, more preferably 5 to 25, very preferably 6 to 18) aromatic ring atoms or a heteroaromatic ring system, which in each case may also be substituted by one or more radicals R'; preferably, R' represents, identically or differently at each occurrence, H, D, F, Cl, Br , I, CN, straight chain alkyl having 1 to 10 C atoms or branched or cyclic alkyl having 3 to 10 C atoms (wherein each case one or more H atoms can be replaced by D or F replacement), or an aromatic or heteroaromatic ring system having 5 to 18 C atoms. According to the present invention, the composition comprises a first host material of formula (H1), a second host material of formula (H2) and a dopant material. The dopant material is preferably a fluorescent emitter. Preferably, the composition comprises at least one fluorescent emitter comprising at least one of the following groups: - containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen arylamines; - bridged triarylamines; - condensed aromatic or heteroaromatic ring systems having at least 14 aromatic ring atoms; - indenoxene, indenoxeneamine or indenoxenediamine; - benzene benzoindenoxene, benzoindenoxineamine or benzoindenoxenediamine; - dibenzoindenoxene, dibenzoindenoxineamine or dibenzoindenoxinediamine; - containing Indenofluorene of a condensed aryl group of two aromatic ring atoms; - bisindenoindenofluorene; - indenodibenzofuran; indenofluoreneamine or indenodiamine; 𠯤; or - a boron derivative. More preferably, the composition comprises at least one fluorescent emitter of one of the following formulas (E-1), (E-2), (E-3) or E-4) as described below:
Figure 02_image103
wherein Ar 10 , Ar 11 , Ar 12 are identically or differently at each occurrence an aromatic or heteroaromatic ring system having 6 to 60 aromatic ring atoms, which may in each case also be replaced by one or more The group R is substituted; the prerequisite for this is that at least one of the groups Ar 10 , Ar 11 , Ar 12 is an aromatic or heteroaromatic ring system with 10 to 40 aromatic ring atoms and contains at least one of 2 to 4 Condensed aryl or heteroaryl groups consisting of condensed aromatic rings, wherein the aromatic or heteroaromatic ring system may be substituted by one or more groups R; R has the same definition as above; and e is 1, 2 , 3 or 4; more preferably, e is 1;
Figure 02_image105
wherein Ar 20 , Ar 21 , Ar 22 are identically or differently at each occurrence an aryl or heteroaryl group having 6 to 30 aromatic ring atoms, which in each case may also be represented by one or more groups R substitution; E 20 at each occurrence is identically or differently selected from BR, C(R 0 ) 2 , Si(R 0 ) 2 , C=O, C=NR 0 , C=C(R 0 ) 2 , O, S, S=O, SO 2 , NR 0 , PR 0 , P(=O)R 0 or P(=S)R 0 ; wherein Ar 20 , Ar 21 and E 20 together form a five-membered ring or a six-membered ring Member ring, and Ar 21 , Ar 22 and E 20 together form a five-member ring or a six-member ring; R 0 represents H, D, F identically or differently at each occurrence, with 1 to 20 (preferably 1 to 20) 10) straight-chain alkyl groups with C atoms or branched or cyclic alkyl groups with 3 to 20 (preferably 3 to 10) C atoms (each of which may be substituted by one or more R groups, wherein in each case one or more non-adjacent CH groups can be replaced by O or S and wherein one or more H atoms can be replaced by D or F), or have 5 to 40 (preferably 5 to 30, more preferably 6 to 18), aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) of aromatic ring atoms, wherein two adjacent radicals The radicals R 0 may together form an aliphatic or aromatic ring system, which may be substituted by one or more radicals R, R having the same definition as above; p, q are identically or differently 0 or 1 at each occurrence , whose prerequisite is p+q=1; r is 1, 2 or 3;
Figure 02_image107
Wherein Ar 30 , Ar 31 , Ar 32 represent identically or differently each occurrence of substituted or unsubstituted aromatic ring atoms having 5 to 22 (preferably 5 to 18, more preferably 6 to 14) aromatic ring atoms. aryl or heteroaryl; E 30 represents B or N; E 31 , E 32 , E 33 represent O, S, C(R 0 ) 2 , C=O, C= S, C=NR 0 , C=C(R 0 ) 2 , Si(R 0 ) 2 , BR 0 , NR 0 , PR 0 , SO 2 , SeO 2 or a chemical bond, the prerequisite is that if E 30 is B, Then at least one of the groups E 31 , E 32 , E 33 represents NR 0 , and if E 30 is N, at least one of the groups E 31 , E 32 , E 33 represents BR 0 ; R 0 has Same definition as above; s, t, u are identically or differently 0 or 1 at each occurrence, with the precondition that s+t+u≥1.
Figure 02_image109
Wherein Ar 40 , Ar 41 , Ar 42 represent identically or differently each occurrence of substituted or unsubstituted aromatic ring atoms having 5 to 22 (preferably 5 to 18, more preferably 6 to 14) aromatic ring atoms. Aryl or heteroaryl; E 41 , E 42 , E 43 represent O, S, C(R 0 ) 2 , C=O, C=S, C=NR 0 , C=C(R 0 ) 2 , Si(R 0 ) 2 , BR 0 , NR 0 , PR 0 , SO 2 , SeO 2 or a chemical bond, the prerequisite being at least one of the groups E 41 , E 42 , E 43 One is present and represents a chemical bond; R 0 has the same definition as above; i, g, h are identically or differently 0 or 1 at each occurrence, with the prerequisite that i+g+h≧1. Preferably, the fluorescent emitter of formula (E-1) comprises at least one group Ar 10 , Ar 11 or Ar 12 , preferably Ar 10 , which is selected from formulas (Ar 10 -1) to (Ar 10 -24) of the group:
Figure 02_image111
Figure 02_image113
Figure 02_image115
wherein the groups Ar 10 -1 to Ar 10 -24 may be substituted at all free positions by one or more groups R; and wherein E 10 at each occurrence is identically or differently selected from BR 0 , C(R 0 ) 2 , Si(R 0 ) 2 , C=O, C=NR 0 , C=C(R 0 ) 2 , O, S, S=O, SO 2 , NR 0 , PR 0 , P(=O) R 0 or P(=S)R 0 , preferably E 10 is C(R 0 ) 2 ; wherein R 0 has the same definition as above; E 11 is selected from C= O, O, S, S=O or SO 2 , preferably O or S, more preferably O; and Ar 13 is, identically or differently in each occurrence, an aromatic having 5 to 60 aromatic ring atoms or heteroaromatic ring systems, which in each case may also be substituted by one or more radicals R. According to a preferred embodiment, the luminophore of formula (E-1) comprises a group Ar 10 , which is selected from groups of formulas (Ar 10 -15) to (Ar 10 -22), wherein d is preferably equal to 1, and preferably at least one of the groups Ar 11 and Ar 12 is a group selected from the formulas (Ar 10 -15) to (Ar 10 -22). According to a very good embodiment, the light-emitting system of formula (E-1) is selected from the light-emitting bodies of formulas (E-1-1) to (E-1-6),
Figure 02_image117
Figure 02_image119
wherein these symbols have the same meanings as above and wherein: f is 0, 1 or 2; and the benzene ring represented in the compounds of the above formulas (E-1-1) to (E-1-6) can be One or more radicals R are substituted at all free positions. Particularly preferably, the compound of formula (E-1) is selected from the compounds of formula (E-1-1-A) to (E-1-6-A),
Figure 02_image121
Figure 02_image123
Figure 02_image125
Wherein these symbols and labels have the same meaning as above, and wherein the benzene rings represented in the compounds of the above formulas (E-1-1-A) to (E-1-6-A) can be passed through one or more A group R is substituted at all free positions. Preferably, the fluorescent light-emitting system of formula (E-2) is selected from the fluorescent emitters of formulas (E-2-1) to (E-2-43),
Figure 02_image127
Figure 02_image129
Figure 02_image131
Figure 02_image133
Figure 02_image135
Figure 02_image137
wherein the groups of formulas (E-2-1) to (E-2-43) may be substituted at all free positions by one or more groups R; and wherein E 20 has the same definition as above. Preferably, E 20 is C(R 0 ) 2 . The compound of formula (E-2) is preferably selected from compounds of formulas (E-2-32) to (E-2-43). More preferably, the compound of formula (E-2) is selected from compounds (E-2-32-A) to (E-2-43-A):
Figure 02_image139
Figure 02_image141
Figure 02_image143
wherein these symbols have the same meanings as above, and wherein the benzene and naphthalene rings represented in the compounds of the above formulas (E-2-32-A) to (E-2-43-A) can be passed through one or more A group R is substituted at all free positions. Preferably, the fluorescent light emitting system of formula (E-3) is selected from the fluorescent light emitters of formula (E-3-1),
Figure 02_image145
Wherein these symbols and labels have the same meanings as above. More preferably, the fluorescent light emitting system of formula (E-3) is selected from the fluorescent light emitters of formula (E-3-2),
Figure 02_image147
wherein the symbols E 30 to E 33 have the same meanings as above; wherein t is 0 or 1, wherein when t is 0, the group E 32 is absent and the group R 10 is present and replaces the bond to E 32 and wherein R 10 represents H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar) 2 , S( =O)Ar, S(=O) 2 Ar, N(R') 2 , N(Ar) 2 , NO 2 , Si(R') 3 , B(OR') 2 , OSO 2 R', with 1 Straight-chain alkyl, alkoxy or alkylthio (thioalkyl) having up to 40 C atoms or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 40 C atoms (each of which can be Substituted by one or more groups R', wherein in each case one or more non-adjacent CH 2 groups can be substituted by R'C=CR', C≡C, Si(R') 2 , Ge( R') 2 , Sn(R') 2 , C=O, C=S, C=Se, P(=O)(R'), SO, SO 2 , O, S or CONR' substitution and one or Multiple H atoms may be replaced by D, F, Cl, Br, I, CN or NO), aromatic or heteroaromatic ring systems with 5 to 60 aromatic ring atoms (which in each case may be replaced by a or multiple groups R'substituted), or an integer of aryloxy groups having 5 to 60 aromatic ring atoms (which may be substituted by one or more groups R'); where two adjacent substituents R 10 may together form an aliphatic or aromatic ring system, which may be substituted by one or more groups R'; wherein R' has the same definition as above. Even more preferably, the fluorescent light emitting system of formula (E-3) is selected from the fluorescent light emitters of formula (E-3-3) and (E-3-4),
Figure 02_image149
Wherein these symbols and labels have the same meanings as above. Preferably, the fluorescent light emitting system of formula (E-4) is selected from the fluorescent light emitters of formula (E-4-1) or (E-4-2),
Figure 02_image151
where E 41 and E 42 represent O, S, C(R 0 ) 2 , C=O, C=S, C=NR 0 , C=C(R 0 ) 2 , Si (R 0 ) 2 , BR 0 , NR 0 , PR 0 , SO 2 , SeO 2 or a chemical bond, wherein E 41 is preferably a bond; R 20 represents H, D, F, Cl identically or differently at each occurrence , Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar) 2 , S(=O)Ar, S(=O) 2 Ar, N(R') 2 , N( Ar) 2 , NO 2 , Si(R') 3 , B(OR') 2 , OSO 2 R', linear alkyl, alkoxy or thioalkyl having 1 to 40 C atoms or Branched or cyclic alkyl, alkoxy or alkylthio groups having 3 to 40 C atoms (each of which may be substituted by one or more radicals R', wherein in each case one or more non-phase The adjacent CH 2 group can be changed by R'C=CR', C≡C, Si(R') 2 , Ge(R') 2 , Sn(R') 2 , C=O, C=S, C= Se, P(=O)(R'), SO, SO 2 , O, S or CONR' replacement and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 ) , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (which in each case may be substituted by one or more radicals R'), or an aromatic ring system having 5 to 60 aromatic ring atoms Oxygen (which may be substituted by one or more groups R'); where two adjacent substituents R may together form an aliphatic or aromatic ring system which may be substituted by one or more groups R'; wherein R' has the same definition as above; g is 0 or 1. More preferably, the fluorescent light-emitting system of formula (E-4) is selected from the fluorescent emitters of formula (E-4-1-A) or (E-4-2-A),
Figure 02_image153
Wherein these symbols have the same meaning as above. According to a preferred embodiment, the fluorescent emitter of formula (E-1), (E-2), (E-3) or (E-4) comprises a group RS, wherein the group RS is: - selected Branched chain or cyclic alkyl represented by the following general formula of the radical of formula (RS-a),
Figure 02_image155
Wherein R 22 , R 23 , R 24 are identically or differently selected from each occurrence of H, straight chain alkyl having 1 to 10 carbon atoms, or branched or cyclic having 3 to 10 carbon atoms Alkyl, wherein each of the aforementioned groups may be substituted by one or more groups R 25 , and wherein two or all of the groups R 22 , R 23 , R 24 may be connected to to form a (poly)cyclic alkyl group, which may be substituted by one or more groups R 25 ; R 25 at each occurrence is identically or differently selected from linear alkyl groups having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms; with the proviso that at each occurrence at least one of the groups R 22 , R 23 and R 24 is not H, with the proviso that At each occurrence, all groups R 22 , R 23 and R 24 together have at least 4 carbon atoms with the proviso that at each occurrence, if two of the groups R 22 , R 23 , R 24 are H, the remaining groups are not linear; or - selected from branched or cyclic alkoxy groups represented by the following general formula (RS-b)
Figure 02_image157
Wherein R 26 , R 27 , R 28 are identically or differently selected from each occurrence of H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic group having 3 to 10 carbon atoms Alkyl, wherein each of the aforementioned groups may be substituted by one or more groups R 25 as defined above, and wherein two or all of the groups R 26 , R 27 , R 28 are R 26 , R 27 , R 28 may be attached to form a (poly)cyclic alkyl group which may be substituted by one or more groups R 25 as defined above; with the proviso that in each occurrence of the groups R 26 , R 27 and R 28 Only one of them can be H; - selected from the aralkyl group represented by the following general formula (RS-c)
Figure 02_image159
Wherein R 29 , R 30 , R 31 are identically or differently selected from each occurrence of H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic group having 3 to 10 carbon atoms Alkyl, wherein the aforementioned groups may each be substituted by one or more groups R 32 , or aromatic ring systems having 6 to 30 aromatic ring atoms which may in each case be substituted by one or more groups R 32 substituted, and wherein two or all of the groups R 29 , R 30 , R 31 can be connected to form a (poly)cyclic alkyl or aromatic ring system, each of which can be connected via one or more groups R 32 is substituted; R 32 is identically or differently selected from straight-chain alkyl groups having 1 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms, or having 6 Aromatic ring systems of up to 24 aromatic ring atoms; provided that at each occurrence at least one of the groups R 29 , R 30 and R 31 is not H, and at each occurrence the group At least one of the groups R 29 , R 30 and R 31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; - selected from the aromatic ring systems represented by the following general formula (RS-d)
Figure 02_image161
wherein R40 to R44 are identically or differently selected from each occurrence of H, linear alkyl having 1 to 10 carbon atoms, or branched or cyclic alkyl having 3 to 10 carbon atoms, wherein the aforementioned radicals may each be substituted by one or more radicals R 32 , or aromatic ring systems having 6 to 30 aromatic ring atoms which may in each case be substituted by one or more radicals R 32 , and wherein two or more of the groups R 40 to R 44 may be linked to form a (poly)cyclic alkyl or aromatic ring system, each of which may be substituted by one or more groups R 32 as defined above or - selected from a group of formula (RS-e),
Figure 02_image163
Wherein the dotted bond in the formula (RS-e) represents the bond to the fluorescent emitter, wherein Ar 50 , Ar 51 represent the same or different aromatic or aromatic ring atoms having 5 to 60 aromatic ring atoms at each occurrence. Heteroaromatic ring systems, which may in each case be substituted by one or more radicals R; and wherein m is an integer selected from 1 to 10. Preferably, the index m in the group of formula (RS-e) is an integer selected from 1 to 6, very preferably selected from 1 to 4. Preferably, wherein Ar 50 , Ar 51 represent identically or differently each occurrence of an aromatic or heteroaryl having 5 to 40 (preferably 5 to 30, more preferably 6 to 18) aromatic ring atoms Acyclic ring systems which may in each case be substituted by one or more radicals R. More preferably, Ar 50 and Ar 51 are selected from phenyl, biphenyl, terphenyl, quaterphenyl, stilbene, spirobistilbene, naphthalene, anthracene, phenanthrene, and triphenylene , allene fluoranthene, dibenzofuran, carbazole and dibenzothiophene, which may in each case be substituted by one or more radicals R. Very preferably, at least one group Ar 50 or Ar 51 is fluorene, which may be substituted by one or more groups R. More particularly, it is preferred that at least one group Ar 50 represents a group of formula (Ar50-2) and/or at least one group Ar 51 represents a group of formula (Ar51-2),
Figure 02_image165
Wherein the dotted line bond in the formula (Ar50-2) represents the bond to the fluorescent light emitter and to the group Ar 50 or Ar 51 ; and the dotted line bond in the formula (Ar51-2) represents the bond to the Ar 50 ; E 4 is selected from -C(R 0a ) 2- , -Si(R 0a ) 2- , -O-, -S- or -N(R 0a )-, preferably -C(R 0a ) 2 ; R 0a H, D, F, CN, straight-chain alkyl having 1 to 40 (preferably 1 to 20, more preferably 1 to 10) C atoms or having 3 to 40 (preferably 3 to 20, more preferably 3 to 10) branched or cyclic alkyl groups of C atoms (each of which may be substituted by one or more groups R), having 5 to 60 (preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18) aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) of aromatic ring atoms ; where two adjacent substituents R 0a can form a monocyclic or polycyclic aliphatic ring system or aromatic ring system, which can be substituted by one or more groups R, which have the same meaning as above; and The groups of the formulas (Ar50-2) and (Ar51-2) may be substituted at each free position by a group R which has the same meaning as above. The group RS is preferably located in a position where RS replaces R, R 0 or R'. Examples of fluorescent emitters that can be used in compositions comprising compounds of the formulas (H1) and (H2) are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic
Figure 111113012-001
Amine (chrysenamine) or aromatic
Figure 111113012-001
diamine. Aromatic anthracenamine means a compound in which one diarylamine group is directly bonded to an anthracenyl group (preferably at the 9-position). Aromatic anthracene diamine means a compound in which two diarylamine groups are directly bonded to an anthracene group (preferably at the 9,10-position). Aromatic pyreneamine, pyrenediamine,
Figure 111113012-001
Amines and
Figure 111113012-001
Diamines are defined analogously thereto, wherein the diarylamine group is preferably bonded to the 1-position or the 1,6-position of pyrene. Further preferred emitters are bridged triarylamines (eg according to WO 2019/111971, WO 2019/240251 and WO 2020/067290). Further preferred emitters are indenoxeneamine or indenoxenediamine (eg according to WO 2006/108497 or WO 2006/122630), benzindenoxeneamine or benzoindenoxenediamine (eg according to WO 2008/ 006449), and dibenzoindenoxeneamine or dibenzoindenoxenediamine (for example according to WO 2007/140847), and the indenoxene derivatives containing condensed aryl groups disclosed in WO 2010/012328. Yet other preferred emitters are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, terpenes linked via heteroaryl groups as in WO 2016/150544 Polymers or phenanthane derivatives as disclosed in WO 2017/028940 and WO 2017/028941. Also preferred are pyrenarylamines disclosed in WO 2012/048780 and WO 2013/185871. Also preferred are the benzoindenotermines disclosed in WO 2014/037077, the benzoindenotermines disclosed in WO 2014/106522 and the ones disclosed in WO 2014/111269 or WO 2017/036574, WO 2018/007421 of indene and fennel. Preferably also as disclosed in WO 2018/095888, WO 2018/095940, WO 2019/076789, WO 2019/170572 and unpublished applications PCT/EP2019/072697, PCT/EP2019/072670 and PCT/EP2019/072662 Emitters containing dibenzofuran or indenodibenzofuran moieties. Also preferred are boron derivatives as disclosed in eg WO 2015/102118, CN108409769, CN107266484, WO2017195669, US2018069182 and unpublished applications EP 19168728.4, EP 19199326.0 and EP 19208643.7. In the context of the present invention, very suitable fluorescent emitters are the indenoxene derivatives disclosed in WO 2018/007421 and the dibenzofuran derivatives disclosed in WO 2019/076789. Examples of preferred fluorescent light-emitting compounds that can be used in compositions comprising compounds of formula (H1) and (H2) are described in the table below:
Figure 02_image167
Figure 02_image169
Figure 02_image171
Figure 02_image173
Figure 02_image175
Figure 02_image177
Figure 02_image179
Figure 02_image181
Figure 02_image183
Figure 02_image185
Figure 02_image187
Figure 02_image189
Figure 02_image191
Figure 02_image193
Figure 02_image195
Figure 02_image197
Figure 02_image199
Figure 02_image201
Figure 02_image203
Figure 02_image205
Figure 02_image207
Figure 02_image209
Figure 02_image211
Figure 02_image213
Figure 02_image215
Figure 02_image217
Figure 02_image219
Figure 02_image221
Figure 02_image223
Figure 02_image225
Figure 02_image227
Figure 02_image229
Figure 02_image231
Figure 02_image233
Figure 02_image235
Figure 02_image237
Figure 02_image239
Figure 02_image241
Figure 02_image243
Figure 02_image245
Figure 02_image247
Figure 02_image249
Figure 02_image251
Figure 02_image253
Figure 02_image255
Figure 02_image257
Figure 02_image259
According to the invention, the compound of formula (H1) and the compound of formula (H2) are present together in a composition, preferably in a homogeneous mixture. Preferably, the compound of formula (H1) is present in the composition at a ratio equal to or higher than 1% by weight of the composition. More preferably, the compound of formula (H1) is present in the composition at a ratio of 1 to 99%, preferably 10 to 95%, more preferably 20 to 90%, particularly preferably 30 to 85%, and very particularly preferably 40 to 80%. middle. Preferably, the compound of formula (H2) is present in the composition at a ratio equal to or higher than 1% by weight of the composition. More preferably, the compound of formula (H2) is present in the composition at a ratio of 1 to 99%, preferably 5 to 90%, more preferably 10 to 80%, particularly preferably 15 to 70%, and very particularly preferably 20 to 60%. middle. According to a preferred embodiment, the composition according to the invention additionally comprises at least one fluorescent emitter. In this case, it is preferred that the fluorescent light-emitting system is present in the composition in a proportion between 0.1 and 50.0%, preferably between 0.5 and 20.0%, particularly preferably between 1.0 and 10.0%. For the purposes of this application, ratio specifications in % mean % by volume if the compound is applied from the gas phase and % by weight if the compound is applied from solution. In order to process the compounds according to the invention from the liquid phase, for example by coating methods such as spin coating or by printing methods, formulations of the compositions according to the invention are required. Such formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it is preferred to use a mixture of two or more solvents. The solvent is preferably selected from organic and inorganic solvents, more preferably organic solvents. The solvent is very preferably selected from hydrocarbons, alcohols, esters, ethers, ketones and amines. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, trimethylbenzene, tetralin, veratrole, THF, methyl-THF , THP, chlorobenzene, dioxane, phenoxytoluene (especially 3-phenoxytoluene), (-)-fenzone, 1,2,3,5-tetramethylbenzene, 1,2,4 ,5-tetramethylbenzene, 1-methylnaphthalene, 1-ethylnaphthalene, decylbenzene, phenylnaphthalene, menthyl isovalerate, p-cresyl isobutyrate, cyclohexal hexanoate ), ethyl p-toluate, ethyl o-toluate, ethyl m-toluate, decahydronaphthalene, ethyl 2-methoxybenzoate, dibutylaniline, dicyclohexyl ketone, isosorbide di Methyl ether, decahydronaphthalene, 2-methylbiphenyl, ethyl octanoate, octyl octanoate, diethyl sebacate, 3,3-dimethylbiphenyl, 1,4-dimethylnaphthalene, 2 ,2'-Dimethylbiphenyl, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4 -Dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, Decalin, Dodecylbenzene, Ethyl Benzoate, Indan, NMP, p-Cymene, Phenylethyl Ether, 1,4-Diisopropylbenzene, Diphenylmethylbenzene Diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether Dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl) Ethane or a mixture of these solvents. The present invention therefore also relates to a formulation comprising a compound of formula (H1 ) and a compound of formula (H2) according to the invention and at least one solvent. The solvent may be one of the above solvents or a mixture of these solvents. The proportion of organic solvents in the formulations according to the invention is preferably at least 60% by weight, preferably at least 70% by weight and better still at least 80% by weight, based on the total weight of the formulation. The formulations according to the invention can be used to produce one-layer or multi-layer structures, wherein organic functional materials can be present in the layers, depending on the requirements for the production of preferred electronic or optoelectronic components, such as OLEDs. The formulations of the invention can preferably be used to form a functional layer comprising a composition according to the invention on a substrate or on one of layers applied to a substrate. Yet another object of the invention is a method of manufacturing an electronic device, wherein at least one layer is obtained from applying the formulation of the invention. Preferably, the formulation according to the invention is applied to a substrate or another layer and then dried. The functional layers obtained from the formulations according to the invention can be coated, for example, by flood coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, rotary printing, roll coating, quick-dry printing ( flexographic printing), lithographic printing or nozzle printing, preferably inkjet printing on the substrate or one of the layers applied to the substrate. After the formulation according to the invention has been applied to the substrate or the applied functional layer, a drying step may be carried out in order to remove the solvent. Preferably, the drying step comprises vacuum drying, which is preferably followed by annealing of the layer. Vacuum drying can preferably be carried out here at a pressure in the range from 10 −7 mbar to 1 bar, particularly preferably at a pressure in the range from 10 −6 mbar to 1 bar. Vacuum drying is preferably performed at a temperature ranging from 10 to 40°C, more preferably 15 to 30°C. The vacuum drying step is preferably followed by thermal annealing of the layer. Thermal annealing of the layers is preferably carried out at a temperature of from 120°C to 180°C, preferably from 130°C to 170°C, more preferably from 140°C to 160°C. Accordingly, the present invention relates to a method of manufacturing an electronic device comprising at least one layer comprising a composition according to the invention, wherein the method comprises the following steps: a) preparing a formulation according to the invention; b) combining the steps The formulation prepared in a) is applied on a substrate or on another layer to form a layer comprising the composition according to the invention; c) drying the layer to remove the solvent. Preferably, in step b), the formulation is produced by processing from the liquid phase, more preferably by a coating method or by a printing method, very preferably by a printing method, particularly preferably by an inkjet printing method apply. Another object of the invention is an electronic device comprising an anode, a cathode and at least one functional layer interposed therebetween, wherein this functional layer comprises a composition according to the invention. Preferably, the at least one functional layer comprising the composition according to the invention is a light-emitting layer. The electronic device is preferably selected from organic electroluminescent devices (OLEDs), organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic dye-sensitized solar cells, organic optical Detectors, organic photoreceptors, organic field quenchers, light emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices. More preferably, the electronic device is an organic electroluminescent device (OLED). An organic electroluminescent device comprises a cathode, an anode and at least one emitting layer comprising a composition according to the invention. Besides these layers, the organic electroluminescent device may also comprise further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, excitonic blocking layer, electron blocking layer, and/or charge generating layer. It is likewise possible to introduce an intermediate layer having, for example, an exciton-blocking function between two emitting layers. However, it should be noted that each of these layers does not necessarily have to be present. The organic electroluminescent device here can comprise an emitting layer or a plurality of emitting layers. If several emitting layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, resulting in white emission overall, ie using various emitting compounds capable of fluorescent or phosphorescent in the luminescent layer. Particularly preferred are systems with three emitting layers, the three layers exhibiting blue, green and orange or red emission (for the basic structure see eg WO 2005/011013). These may be fluorescent or phosphorescent emitting layers or hybrid systems in which fluorescent and phosphorescent emitting layers are combined with one another. The electronic device concerned may comprise a single light-emitting layer comprising the composition according to the invention, or it may comprise two or more light-emitting layers. Compositions according to the invention may comprise one or more other matrix materials. Preferred further matrix materials are selected from the following classes: oligoarylene (eg 2,2',7,7'-tetraphenylspirobistilbene or dinaphthylanthracene according to EP 676461), in particular are oligoarylene containing condensed aromatic groups, oligoarylenevinylene (eg DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (eg according to WO 2004/081017), hole-conducting compounds (for example according to WO 2004/058911), electron-conducting compounds, especially ketones, phosphine oxides, phosphine, etc. (for example according to WO 2005/084081 and WO 2005/084082), atropine Isomers (eg according to WO 2006/048268), boronic acid derivatives (eg according to WO 2006/117052), or benzanthracene (eg according to WO 2008/145239). Particularly preferred host materials are selected from the following classes: oligoarylene, oligoarylene vinylene, ketone, oxidized Phosphine and Phosphine. Very particularly preferred matrix materials are selected from the class of oligoarylenes comprising anthracene, benzanthracene, triphenanthrene and/or pyrene or atropisomers of these compounds. An oligoaryl group in the sense of the present invention means a compound in which at least three aryl groups or aryl groups are bonded to one another. Generally preferred classes of materials used as corresponding functional materials in organic electroluminescent devices according to the invention are indicated below. Suitable charge transport materials, such as can be used in hole injection or hole transport layers or electron blocking layers of electronic devices according to the invention or in electron transport layers are, for example, Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials used in these layers according to the prior art. Materials which can be used for the electron-transport layer are all materials which have been used according to the prior art as electron-transport materials in the electron-transport layer. Particularly suitable are aluminum complexes (for example, Alq 3 ), zirconium complexes (for example, Zrq 4 ), lithium complexes (for example LiQ), benzimidazole derivatives, trioxane derivatives, pyrimidine derivatives, Pyridine derivatives, pyridine derivatives, quinoline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives. Furthermore, suitable materials are derivatives of the aforementioned compounds, as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300. Preferred hole transport materials which can be used in the hole transport layer, hole injection layer or electron blocking layer in the electroluminescent device according to the invention are indenoximide derivatives (for example according to WO 06/122630 or WO 06 /100896), amine derivatives disclosed in EP 1661888, hexaazabistriphenylene derivatives (for example according to WO 01/049806), amine derivatives containing condensed aromatic rings (for example according to US 5,061,569), WO 95/ Amine derivatives disclosed in 09147, monobenzindenoxylamine (eg according to WO 08/006449), dibenzoindenoxylamine (eg according to WO 07/140847), spirobistilamine (eg according to WO 2012 /034627 or WO 2013/120577), stilamine (eg according to applications EP 2875092, EP 2875699 and EP 2875004), spirodibenzopyranylamine (eg according to WO 2013/083216) and dihydroacridine derivatives (eg According to WO 2012/150001). The compounds according to the invention can also be used as hole transport materials. The cathode of an organic electroluminescent device preferably comprises a metal with a low work function, a metal alloy or a multilayer structure comprising various metals, such as, for example, alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg , Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising alkali metals or alkaline earth metals and silver, for example alloys comprising magnesium and silver. In the case of multilayer structures, besides these metals, other metals with higher work functions can also be used, such as, for example, Ag or Al, in which case a combination of metals is usually used, such as, for example, Ca/Ag , Mg/Ag or Ag/Ag. It may also be advantageous to introduce a thin interlayer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal fluorides or alkaline earth metal fluorides, but corresponding oxides or carbonates (such as LiF, Li 2 O, BaF 2 , MgO, NaF, CsF, Cs 2 CO 3 , etc. ) is also suitable. Additionally, lithium quinolinate (LiQ) can be used for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm. The anode preferably comprises a material with a high work function. The anode preferably has a work function greater than 4.5 eV versus vacuum. Suitable for this purpose are on the one hand metals with a high redox potential, such as, for example, Ag, Pt or Au. On the other hand, metal/metal oxide electrodes such as Al/Ni/ NiOx , Al/ PtOx may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to facilitate illumination of organic materials (organic solar cells) or coupling-out of light (OLEDs, O-lasers). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). In addition, conductive doped organic materials are preferred, especially conductive doped polymers. The device is structured appropriately (depending on the application), equipped with joints and finally sealed, since the lifetime of the device according to the invention is shortened in the presence of water and/or air. In a preferred embodiment, the organic electroluminescent device according to the invention is characterized in that one or more layers are coated by means of a sublimation method, wherein the materials are applied in a vacuum sublimation unit at temperatures below 10-5 mbar, more Preferably applied by vapor deposition at an initial pressure below 10-6 mbar. However, the initial pressure can also be even lower here, for example below 10-7 mbar. Also preferred is an organic electroluminescent device characterized in that one or more layers are coated by the OVPD (Organic Vapor Phase Deposition) method or supplemented by a carrier-gas sublimation method, wherein the materials are between 10 -5 mm applied at a pressure between bar and 1 bar. A particular example of this method is the OVJP (Organic Vapor Jet Printing) method, in which the materials are applied directly through nozzles and thus structured (e.g. MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301). Further preferred is an organic electroluminescent device characterized in that one or more layers are formed such as, for example, by spin coating or by any desired printing method, such as, for example, screen printing, fast-dry printing, nozzle printing or lithography Printing, but particularly preferably LITI (Light Induced Thermal Imaging, Thermal Transfer Printing) or inkjet printing) from solution. Soluble compounds of formula (I) are required for this purpose. High solubility can be achieved through appropriate substitution of these compounds. Hybrid methods are also possible in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition. Thus, for example, it is possible to apply the emitting layer from solution and the electron-transporting layer by vapor deposition. These methods are generally known to the person skilled in the art and can be applied by the person skilled in the art to organic electroluminescent devices comprising the compounds according to the invention without inventive step. According to the invention, electronic devices comprising one or more compounds according to the invention can be used in displays, as light sources in lighting applications, and as light sources in medical and/or cosmetic applications such as phototherapy. The invention will now be explained in more detail with the following examples, without wishing to limit the invention thereby.

合成例 a) 主體H1 式(H1)的主體之合成為熟習此項技術者已知且描述於例如WO 2010/135395、WO 2019/065415和WO 2020/096053中。以下描述其他合成例： H1-1的合成

Figure 02_image261
將10 g (19.7 mmol) 7-乙基-4-(10-苯基蒽-9-基)四芬(tetraphene)溶解在230 mL甲苯-D8中。滴加10.4 ml (0.12 mol)三氟甲磺酸並將混合物在室溫下攪拌。二小時後，添加47 ml D 2O並將混合物攪拌10分鐘，直至將其加至磷酸鉀水溶液中。用甲苯萃取混合物，用硫酸鈉乾燥合併的有機相。在減壓下減少有機相。將剩餘的固體藉由管柱層析和從二氯甲烷：環己烷和甲苯：正庚烷中多次結晶純化至高達99.9%的HPLC純度。產量5.7 g (10.8 mmol，55%)。 可以類似的方式合成下列化合物：
Figure 02_image263
H1-3的合成：
Figure 02_image265
將15 g (38 mmol) 三氟-甲磺酸8-溴-二苯并呋喃-1-基酯、34.9 g (114 mmol) 2414494-83-8 (WO2020071478)、35.5 g (167 mmol) 磷酸鉀和1.6 g (1,9 mmol) XPhos Palladacycle Gen. 3溶解在450 ml THF/水(2：1)中。將混合物在90℃下攪拌16小時。冷卻至室溫後，添加300 ml乙醇並將混合物攪拌一小時。濾出沈澱物並用乙醇洗滌。將原料溶解在甲苯中並通過濾塞(二氧化矽，甲苯)過濾以產生黃色固體，將其藉由從甲苯/庚烷中多次結晶而進一步純化以產生淡黃色固體(HPLC ＞99.9)。藉由昇華(在330℃下10 -5巴)移除剩餘的溶劑。 產量：14.1 g (20.4 mmol；54%) H1-5的合成
Figure 02_image267
在氬氛圍下，將烘箱乾燥的燒瓶配備磁力攪拌棒、 1(2417686-30-5) (13.0 g，36.9 mmol，1.0 equiv.)、 2(237545-68-9) (18.4 g，54 mmol)、參(二苯亞甲基丙酮)二鈀(1.3 g，1.4 mmol)、SPhos (1.16 g，2.8 mmol)和氟化鉀(5.3 g，92.3 mmol)。添加甲苯(150 mL)、1,4-二㗁烷(150 mL)和水(150 mL)並將混合物加熱回流過夜。將原產物藉由管柱層析和昇華純化。分離出所欲產物的白色固體(5.1 g，8.9 mmol，24%)。 a) 主體H2 式(H2)的主體之合成為熟習此項技術者已知且描述於例如WO 2009/100925、WO 2018/150832和KR2018131963中。以下描述其他合成例： 化合物H2-1的合成：
Figure 02_image269
將7.9 g (32 mmol) 3,6-二氯-菲(20851-90-5)、30.4 g (80 mmol) 4,4,5,5-四甲基-2-(10-苯基-9-蒽基)-1,3,2-二氧硼雜環戊烷(dioxaborolane)(460347-59-5)和29.5 g (128 mmol)磷酸鉀單水合物溶解於750 ml THF/水(2：1)。添加813 mg (0.96 mmol) XPhos Palladacycle Gen. 3，並在65℃下攪拌混合物。16小時後，使反應混合物回到室溫。將反應混合物過濾及以冷THF洗滌。將沉澱物藉由於氧化鋁上熱萃取(甲苯)純化並以甲苯/乙醇和甲苯/庚烷結晶來進一步純化，至以HPLC測得高達＞99.9%之純度。藉由在300℃和10-5巴下回火2小時以去除剩餘的溶劑。 產量：4.9 g (7.2 mmol，23%)的淡黃色固體 可以類似的方式合成下列化合物：
Figure 02_image271
OLED的製造 a) 薄膜和裝置的製備 使用超音波將覆蓋有預結構化的ITO (50 nm)和空白材料之玻璃基板於去離子水中清潔。下文中，基板係使用空氣槍乾燥及接著在加熱板上於230℃退火2小時。 所有下列方法步驟係於黃光中進行。 下列層順序顯示於圖4a和4b中。 將電洞注入層(HIL)以20 nm的厚度噴墨印刷於基板上，並在真空下乾燥。為此，HIL油墨具有6 g/l的固體濃度。接著將HIL在220℃下退火30分鐘。HIL的噴墨印刷和退火是在空氣中進行。作為HIL材料，將電洞傳輸性之可交聯的聚合物和經p-摻雜的鹽溶解於3-苯氧基甲苯中。這些材料係描述於例如WO2016/107668、WO2013/081052和EP2325190中。 在HIL的上部，在環境條件下噴墨印刷電洞傳輸層，在真空中乾燥及於氬氛圍中在225℃下退火30分鐘。電洞傳輸層為表1中所示結構的聚合物(HTM1)(其係根據WO2013156130合成)或聚合物HTM2 (表1)(其係根據 WO2018/114882合成)。將聚合物溶解於3-苯氧基甲苯中，使得在此若利用噴墨印刷欲達到裝置之典型的20 nm層厚度，則溶液通常具有約5 g/l的固體含量。 發光層包含如下表2中所述之基質材料(一種主體化合物或二種主體化合物)和摻雜劑。將用於發光層的混合物溶解於3-苯氧基甲苯中。在此若利用噴墨印刷欲達到裝置之典型的30 nm層厚度，則該等溶液的固體含量為10 mg/ml。也將藍色發光層(B-EML)噴墨印刷，接著真空乾燥及在150℃下退火10分鐘。噴墨印刷係在環境氛圍下進行，而退火是在氬氛圍下進行。 根據製備圖4a的裝置係使用於評估EML薄膜的均勻性。 為了製備用於電光示性的根據圖4b之裝置，則將樣品轉移至真空沉積室中，在其中使用熱蒸發進行兩個電子傳輸層(ETL1、ETL2)、電子注入層(EIL)和陰極(Al)的沉積。如此，ETL1係由ETM1 (10 nm薄膜厚度)組成，而ETL2係由ETM1和ETM2之1：1體積%混合物(35 nm薄膜厚度)組成。電子注入層由ETM2 (1 nm)組成，及陰極為鋁(100 nm)。結構顯示於表1中。 蒸發後，在氬氛圍的手套箱中封裝裝置。
Figure 02_image273
b) 發光薄膜均勻性之評估 對於顯示器的製造，非常重要的是得到非常良好的像素均勻性且同時具有良好的裝置性能。層厚度的不均勻性造成不均勻的發光強度分佈，薄膜厚度較薄的區域顯示發光強度增加，而較厚的區域顯示發光強度減少。不均勻性隨著像素不同而變化，從而像素之間的可再現外觀無法得到。綜合而言，此將導致對該類顯示器的品質有負面看法。因此，本發明針對EML薄膜均勻性和裝置性能的課題。從而，評估的第一步為檢測薄膜均勻性。為此，使用圖4a所示的堆疊。在EML沉積後停止處理。薄膜係如a)部分中所述製備。EML的組成示於表2a和表2b中。 為了評估印刷薄膜的均勻性，印刷薄膜的形貌係以輪廓儀(profilometer)沿著10 µm輪廓特性化，並計算
Figure 02_image275
(峰至谷)值以及粗糙度的均方根差。使用來自KLA-Tencor Corporation之配備2 μm記錄針的輪廓儀Alpha-step D120測量薄膜輪廓。
Figure 02_image275
值對應於在所測量的輪廓內之測得的最大峰和最小峰之高度差。為了便於查看，減去薄膜輪廓的基線，使得最小峰對應於0 nm高度且所有圖的軸刻度均相同。 下列二個方程式係用於決定薄膜均勻性。峰至谷差值
Figure 02_image275
表示層內之最大高度差(方程式1)，及均方根的粗糙度RMS，其中
Figure 02_image277
對應於在i位置的輪廓高度，及
Figure 02_image279
對應於平均輪廓高度(方程式2)。
Figure 02_image281
Figure 02_image283
相較於其中僅使用主體組分2之PR1，包含根據本發明之主體混合物的實施例PE1顯示顯著減少的
Figure 02_image285
，且因此對應於更平滑的薄膜(圖1和3)。 此外，實施例PE1呈現與參考例PR2類似的
Figure 02_image285
值，但其導致顯著更好的OLED性能，如表5a中所示(DE1相對於DR1)。 總而言之，只有混合主體系統能夠實現同時具有良好均勻性和良好裝置性能(EQE和LT)的光滑薄膜。 另外發光層(EML)之其他薄膜均勻性係顯示於下表2b中。
Figure 02_image287
在基於混合主體系統的所有發光層輪廓的情況下，
Figure 02_image285
值係顯著低於以主體組分1為主之各個單一主體EML的值(PE2相對於PR4；PE3相對於PR6；PE4和PE5相對於PR8；PE6相對於PR10；PE7相對於PR12)。相較於以單一主體組分2為主之各個EML，根據本發明之EML (混合主體系統)的
Figure 02_image285
值係在相似的範圍內。在這些情況下，本發明的優勢為較佳的裝置性能(EQE或LT)，如下述裝置結果章節所說明(參見表5a至5e)。 c) 裝置結果 如圖4b中所示的裝置係根據a)部份製備。主體材料係顯示於表3中及發光體係顯示於表4中。藍色EML油墨係根據表5a至5e和表6a至6c混合。 為了測定所製造的OLED之裝置性能，彼等以標準方法示性。為此目的，記錄電致發光光譜、假設Lambert發光特性的電流/電壓/發光密度特徵曲線(IUL特徵曲線)、和(操作)壽命。IUL特徵曲線係用於確定諸如在某發光強度下的外部量子效率(以%表示)的優點之特徵圖。在施加電壓斜坡的各步驟以恒電壓驅動裝置。在對應於初始發光強度的給定電流下測量裝置壽命。接著利用校正過的光二極體測量隨時間變化的發光強度。 在表5a至5e中，總結EML的相對外部量子效率(在1000 cd/m 2下的相對EQE)和相對裝置壽命(在1000 cd/m 2下的相對LT90)，其輪廓在表2a和2b中進行研究。
Figure 02_image289
Figure 02_image291
Figure 02_image293
Figure 02_image295
Figure 02_image297
Figure 02_image299
Figure 02_image301
Figure 02_image303
相較於以主體組分2為主之各個單一主體EML，所示之混合主體系統的實施例全部呈現改良的裝置性能。相較於以主體組分1為主之單一主體EML，混合主體系統的裝置性能是相當的。然而，在這些情況下，達到改良的薄膜均勻性，如表2a和2b中所示。 總而言之，本發明(即混合主體EML)能夠實現同時具有良好均勻性和良好裝置性能(EQE和LT)的光滑薄膜。 具有良好薄膜均勻性和良好裝置性能的其他混合主體EML例係總結於表6a至6c中。
Figure 02_image305
Figure 02_image307
Figure 02_image309
Synthesis examples a) Hosts H1 The synthesis of hosts of the formula (H1) is known to those skilled in the art and is described eg in WO 2010/135395, WO 2019/065415 and WO 2020/096053. Other synthesis examples are described below: Synthesis of H1-1
Figure 02_image261
10 g (19.7 mmol) of 7-ethyl-4-(10-phenylanthracen-9-yl)tetraphene were dissolved in 230 mL of toluene-D8. 10.4 ml (0.12 mol) of trifluoromethanesulfonic acid were added dropwise and the mixture was stirred at room temperature. After two hours, 47 ml D2O was added and the mixture was stirred for 10 minutes until it had been added to the aqueous potassium phosphate solution. The mixture was extracted with toluene and the combined organic phases were dried over sodium sulfate. The organic phase was reduced under reduced pressure. The remaining solid was purified by column chromatography and multiple crystallizations from dichloromethane:cyclohexane and toluene:n-heptane up to 99.9% HPLC purity. Yield 5.7 g (10.8 mmol, 55%). The following compounds can be synthesized in a similar manner:
Figure 02_image263
Synthesis of H1-3:
Figure 02_image265
15 g (38 mmol) 8-bromo-dibenzofuran-1-yl trifluoro-methanesulfonate, 34.9 g (114 mmol) 2414494-83-8 (WO2020071478), 35.5 g (167 mmol) potassium phosphate and 1.6 g (1,9 mmol) XPhos Palladacycle Gen. 3 were dissolved in 450 ml THF/water (2:1). The mixture was stirred at 90°C for 16 hours. After cooling to room temperature, 300 ml of ethanol were added and the mixture was stirred for one hour. The precipitate was filtered off and washed with ethanol. The material was dissolved in toluene and filtered through a filter plug (silica, toluene) to yield a yellow solid, which was further purified by multiple crystallization from toluene/heptane to yield a pale yellow solid (HPLC >99.9). The remaining solvent was removed by sublimation (10 −5 bar at 330° C.). Yield: 14.1 g (20.4 mmol; 54%) Synthesis of H1-5
Figure 02_image267
Oven-dried flask equipped with magnetic stir bar, 1 (2417686-30-5) (13.0 g, 36.9 mmol, 1.0 equiv.), 2 (237545-68-9) (18.4 g, 54 mmol) under argon atmosphere , ginseng(dibenzylideneacetone)dipalladium (1.3 g, 1.4 mmol), SPhos (1.16 g, 2.8 mmol) and potassium fluoride (5.3 g, 92.3 mmol). Toluene (150 mL), 1,4-dioxane (150 mL) and water (150 mL) were added and the mixture was heated to reflux overnight. The crude product was purified by column chromatography and sublimation. The desired product was isolated as a white solid (5.1 g, 8.9 mmol, 24%). a) Hosts H2 The synthesis of hosts of formula (H2) is known to the person skilled in the art and is described, for example, in WO 2009/100925, WO 2018/150832 and KR2018131963. Other synthesis examples are described below: Synthesis of compound H2-1:
Figure 02_image269
7.9 g (32 mmol) 3,6-dichloro-phenanthrene (20851-90-5), 30.4 g (80 mmol) 4,4,5,5-tetramethyl-2-(10-phenyl-9 -Anthracenyl)-1,3,2-dioxaborolane (dioxaborolane) (460347-59-5) and 29.5 g (128 mmol) of potassium phosphate monohydrate were dissolved in 750 ml THF/water (2: 1). 813 mg (0.96 mmol) XPhos Palladacycle Gen. 3 were added and the mixture was stirred at 65°C. After 16 hours, the reaction mixture was allowed to return to room temperature. The reaction mixture was filtered and washed with cold THF. The precipitate was purified by hot extraction (toluene) on alumina and further purified by crystallization from toluene/ethanol and toluene/heptane to a purity of up to >99.9% by HPLC. The remaining solvent was removed by tempering at 300° C. and 10 −5 bar for 2 hours. Yield: 4.9 g (7.2 mmol, 23%) of a light yellow solid The following compounds can be synthesized in a similar manner:
Figure 02_image271
Fabrication of OLEDs a) Preparation of thin films and devices Glass substrates covered with pre-structured ITO (50 nm) and blank material were cleaned in deionized water using ultrasound. Hereinafter, the substrates were dried using an air gun and then annealed on a hot plate at 230° C. for 2 hours. All following method steps were performed under yellow light. The following layer sequence is shown in Figures 4a and 4b. A hole injection layer (HIL) was inkjet printed on the substrate with a thickness of 20 nm and dried under vacuum. For this purpose, the HIL ink has a solids concentration of 6 g/l. The HIL was then annealed at 220°C for 30 minutes. Inkjet printing and annealing of HIL were carried out in air. As HIL material, a hole-transporting crosslinkable polymer and a p-doped salt were dissolved in 3-phenoxytoluene. These materials are described eg in WO2016/107668, WO2013/081052 and EP2325190. On top of the HIL, the hole transport layer was inkjet printed under ambient conditions, dried in vacuum and annealed at 225° C. for 30 minutes in an argon atmosphere. The hole transport layer is a polymer (HTM1) with the structure shown in Table 1 (synthesized according to WO2013156130) or a polymer HTM2 (Table 1) (synthesized according to WO2018/114882). The polymer is dissolved in 3-phenoxytoluene such that the solution generally has a solids content of about 5 g/l if a typical layer thickness of 20 nm of the device is to be achieved by means of inkjet printing. The light-emitting layer contained a host material (one host compound or two host compounds) and a dopant as described in Table 2 below. The mixture used for the light-emitting layer was dissolved in 3-phenoxytoluene. The solutions have a solids content of 10 mg/ml if the typical layer thickness of 30 nm of the device is to be achieved by means of inkjet printing. The blue light-emitting layer (B-EML) was also inkjet printed, followed by vacuum drying and annealing at 150° C. for 10 minutes. Inkjet printing was performed under ambient atmosphere, while annealing was performed under argon atmosphere. The apparatus prepared according to Fig. 4a was used to evaluate the homogeneity of EML thin films. In order to prepare the device according to Figure 4b for electro-optic characterization, the sample was transferred to a vacuum deposition chamber where two electron transport layers (ETL1, ETL2), electron injection layer (EIL) and cathode ( Al) deposition. Thus, ETL1 consists of ETM1 (10 nm film thickness), while ETL2 consists of a 1:1 volume % mixture of ETM1 and ETM2 (35 nm film thickness). The electron injection layer is composed of ETM2 (1 nm), and the cathode is aluminum (100 nm). The structures are shown in Table 1. After evaporation, the device was packaged in a glove box under an argon atmosphere.
Figure 02_image273
b) Evaluation of uniformity of luminescent film For the manufacture of displays, it is very important to obtain very good pixel uniformity and at the same time have good device performance. Inhomogeneity in layer thickness results in a non-uniform luminous intensity distribution, with regions of thinner film thickness showing increased luminous intensity and thicker regions showing decreased luminous intensity. The non-uniformity varies from pixel to pixel so that reproducible appearance between pixels cannot be obtained. Taken together, this will lead to a negative perception of the quality of this type of display. Therefore, the present invention addresses the issues of EML film uniformity and device performance. Thus, the first step in the evaluation is to check the film uniformity. For this, the stack shown in Figure 4a is used. Treatment was stopped after EML deposition. Films were prepared as described in part a). The composition of EML is shown in Table 2a and Table 2b. In order to evaluate the uniformity of the printed film, the topography of the printed film was characterized with a profilometer along a 10 µm profile, and the calculated
Figure 02_image275
(Peak-to-valley) value and root mean square difference of roughness. Film profiles were measured using a profiler Alpha-step D120 from KLA-Tencor Corporation equipped with a 2 μm stylus.
Figure 02_image275
The values correspond to the difference in height between the largest and smallest peaks measured within the measured profile. For ease of viewing, the baseline of the film profile was subtracted such that the smallest peak corresponds to 0 nm height and the axis scales are the same for all plots. The following two equations are used to determine film uniformity. peak-to-valley difference
Figure 02_image275
Represents the maximum height difference within a layer (Equation 1), and the root mean square roughness RMS, where
Figure 02_image277
corresponds to the profile height at position i, and
Figure 02_image279
Corresponds to the mean profile height (Equation 2).
Figure 02_image281
Figure 02_image283
Example PE1 comprising the host mixture according to the invention showed a significantly reduced
Figure 02_image285
, and thus correspond to smoother films (Figs. 1 and 3). In addition, Example PE1 exhibits a similar
Figure 02_image285
values, but it leads to significantly better OLED performance, as shown in Table 5a (DE1 vs. DR1). All in all, only hybrid host systems are able to achieve smooth films with both good homogeneity and good device performance (EQE and LT). Additional film uniformity for the emissive layer (EML) is shown in Table 2b below.
Figure 02_image287
In the case of all emissive layer profiles based on mixed host systems,
Figure 02_image285
The values were significantly lower than those of the individual single-subject EMLs dominated by subject component 1 (PE2 relative to PR4; PE3 relative to PR6; PE4 and PE5 relative to PR8; PE6 relative to PR10; PE7 relative to PR12). Compared with each EML based on a single host component 2, the EML (mixed host system) according to the present invention
Figure 02_image285
The values are in a similar range. In these cases, the advantage of the present invention is better device performance (EQE or LT), as illustrated in the Device Results section below (see Tables 5a to 5e). c) Device Results The device shown in Figure 4b was prepared according to part a). The host materials are shown in Table 3 and the luminescent systems are shown in Table 4. The blue EML ink was mixed according to Tables 5a to 5e and Tables 6a to 6c. In order to determine the device performance of the fabricated OLEDs, they were characterized by standard methods. For this purpose, the electroluminescence spectrum, the current/voltage/luminous density characteristic curve (IUL characteristic curve) assuming the Lambert luminescence characteristic, and the (operating) lifetime are recorded. The IUL characteristic curve is a characteristic diagram used to determine advantages such as external quantum efficiency (expressed in %) at a certain luminous intensity. The device was driven at a constant voltage at each step of applying a voltage ramp. The device lifetime was measured at a given current corresponding to the initial luminous intensity. The luminous intensity over time is then measured using the calibrated photodiode. In Tables 5a to 5e, the relative external quantum efficiencies (relative EQE at 1000 cd/ m2 ) and relative device lifetimes (relative LT90 at 1000 cd/ m2 ) of EMLs are summarized, with profiles in Tables 2a and 2b research in.
Figure 02_image289
Figure 02_image291
Figure 02_image293
Figure 02_image295
Figure 02_image297
Figure 02_image299
Figure 02_image301
Figure 02_image303
The illustrated embodiments of the mixed host systems all exhibit improved device performance compared to each single host EML based on host component 2. Compared to the single-host EML with host component 1 as the main component, the device performance of the mixed-host system was comparable. In these cases, however, improved film uniformity was achieved, as shown in Tables 2a and 2b. In summary, the present invention (ie hybrid host EML) enables smooth thin films with both good homogeneity and good device performance (EQE and LT). Other hybrid host EML examples with good film uniformity and good device performance are summarized in Tables 6a to 6c.
Figure 02_image305
Figure 02_image307
Figure 02_image309

[圖1]：顯示薄膜輪廓PR1。 [圖2]：顯示薄膜輪廓PR2。 [圖3]：顯示薄膜輪廓PE1。 [圖4a]：用於評估發光層之薄膜均勻性的裝置之堆疊。 [圖4b]：用於評估裝置之性能的裝置之堆疊。 [Fig. 1]: The film profile PR1 is displayed. [Fig. 2]: The film profile PR2 is displayed. [Fig. 3]: The film profile PE1 is shown. [FIG. 4a]: A stack of devices for evaluating the thin film uniformity of the light-emitting layer. [Fig. 4b]: Stack of devices used to evaluate the performance of the devices.

Claims (20)

一種用於發光層之組成物，其包含： 式(H1)之第一主體材料，
Figure 03_image001
式(H2)之第二主體材料，
Figure 03_image003
及摻雜劑材料； 其中下列適用於所使用的符號和標號： G 1為具有6至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R X取代； G 2係選自式(G2)之基團：
Figure 03_image005
其中基團E為選自下列之二價橋；-Y=Y-、-C(R B0) 2-、Si(R B0) 2-、-O-、-S-、-C(=O)-、-S(=O)-、-SO 2-、-BR B0-、-N(R B0)-或-P(R B0)-；及其中R B0在每次出現時相同或不同地代表H、F、CN、具有1至40個C原子之直鏈烷基或具有3至40個C原子之支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)；其中二個相鄰的取代基R B0可形成單環或多環的脂族環系統或芳族環系統，其可經一或多個基團R取代； Y    在每次出現時相同或不同地代表C-R Y或N；其先決條件為當Y鍵結至基團Ant 2時，Y代表C； Ant 1為式(A1)之基團：
Figure 03_image007
其中式(A1)中之虛線鍵表示至基團G 1的鍵結位置，及其中基團Ant 1可鍵結至G 1的任何自由位置； Ant 2為式(A2)之基團：
Figure 03_image009
其中式(A2)中之虛線鍵表示至基團G 2的鍵結位置，及其中基團Ant 2可鍵結至G 2的任何自由位置； Ar A1、Ar B1、Ar AS、Ar BS在每次出現時相同或不同地為具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R取代； R A1至R A8、R B1至R B8、R Y、R X在每次出現時相同或不同地代表選自下列之基團：H、D、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R) 2、N(Ar) 2、NO 2、Si(R) 3、B(OR) 2、OSO 2R、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基(thioalkyl)或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R取代，其中在各情況下一或多個非相鄰的CH 2基團可經RC=CR、C≡C、Si(R) 2、Ge(R) 2、Sn(R) 2、C=O、C=S、C=Se、P(=O)(R)、SO、SO 2、O、S或CONR置換及其中一或多個H原子可經D、F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)、和具有5至60個芳族環原子之芳氧基(其可經一或多個基團R取代)； 其先決條件為R B1至R B8和R Y不代表D；及 其中二個相鄰的基團R A1至R A8、R B1至R B8、R Y或R X可一起形成脂族、芳族或雜芳族環系統，其可經一或多個基團R取代； R    在每次出現時相同或不同地代表H、D、F、Cl、Br、I、CHO、CN、C(=O)Ar、P(=O)(Ar) 2、S(=O)Ar、S(=O) 2Ar、N(R’) 2、N(Ar) 2、NO 2、Si(R’) 3、B(OR’) 2、OSO 2R’、具有1至40個C原子之直鏈烷基、烷氧基或烷硫基或具有3至40個C原子之支鏈或環狀烷基、烷氧基或烷硫基(彼等各自可經一或多個基團R’取代，其中在各情況下一或多個非相鄰的CH 2基團可經R’C=CR’、C≡C、Si(R’) 2、Ge(R’) 2、Sn(R’) 2、C=O、C=S、C=Se、P(=O)(R’)、SO、SO 2、O、S或CONR’置換及其中一或多個H原子可經D、F、Cl、Br、I、CN或NO 2置換)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R’取代)、或具有5至60個芳族環原子之芳氧基(其可經一或多個基團R’取代)；其中二個相鄰的取代基R可一起形成脂族或芳族環系統，其可經一或多個基團R’取代； Ar   在每次出現時相同或不同地為具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R’取代； R’ 在每次出現時相同或不同地代表H、D、F、Cl、Br、I、CN、具有1至20個C原子之直鏈烷基、烷氧基或烷硫基或具有3至20個C原子之支鏈或環狀烷基、烷氧基、或烷硫基(其中在各情況下一或多個非相鄰的CH 2基團可經SO、SO 2、O、S置換及其中一或多個H原子可經D、F、Cl、Br或I置換)、或具有5至24個芳族環原子之芳族或雜芳族環系統；及 n    在每次出現時相同或不同地為0或1；其中當n為0時，則對應Ar AS或Ar BS不存在，及蒽基係直接鍵結至基團G 1或G 2； m為0或1； 其特徵在於式(H1)化合物包含至少一個氘原子，及式(H2)化合物實質上不含氘原子。 A composition for a light-emitting layer, comprising: a first host material of formula (H1),
Figure 03_image001
The second host material of formula (H2),
Figure 03_image003
and dopant materials; wherein the following applies to the symbols and designations used: G is an aromatic or heteroaromatic ring system having 6 to 60 aromatic ring atoms, which in each case may also be via one or more A group R X is substituted; G 2 is a group selected from formula (G2):
Figure 03_image005
Wherein the group E is a divalent bridge selected from the following; -Y=Y-, -C(R B0 ) 2 -, Si(R B0 ) 2 -, -O-, -S-, -C(=O) -, -S(=O)-, -SO 2 -, -BR B0 -, -N(R B0 )-, or -P(R B0 )-; and wherein R B0 represents identically or differently at each occurrence H, F, CN, linear alkyl having 1 to 40 C atoms or branched or cyclic alkyl having 3 to 40 C atoms (each of which may be substituted by one or more radicals R), Aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) having 5 to 60 aromatic ring atoms; where two adjacent substituents R B0 can form a monocyclic ring or polycyclic aliphatic ring system or aromatic ring system, which may be substituted by one or more groups R; Y at each occurrence represents CRY or N identically or differently; the prerequisite for this is that when Y is bonded When arriving at group Ant 2 , Y represents C; Ant 1 is the group of formula (A1):
Figure 03_image007
Wherein the dotted line bond among the formula (A1) represents to the bonding position of group G 1 , and wherein group Ant 1 can be bonded to any free position of G 1 ; Ant 2 is the group of formula (A2):
Figure 03_image009
Wherein the dotted line bond in the formula (A2) represents the bonding position to the group G 2 , and wherein the group Ant 2 can be bonded to any free position of G 2 ; Ar A1 , Ar B1 , Ar AS , Ar BS in each Identical or different occurrences of an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R A1 to R A8 , R B1 to R B8 , RY , R X identically or differently represent at each occurrence a group selected from the group consisting of: H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar , P(=O)(Ar) 2 , S(=O)Ar, S(=O) 2 Ar, N(R) 2 , N(Ar) 2 , NO 2 , Si(R) 3 , B(OR ) 2 , OSO 2 R, straight-chain alkyl, alkoxy or thioalkyl having 1 to 40 C atoms or branched or cyclic alkyl and alkoxy having 3 to 40 C atoms or alkylthio groups (each of which may be substituted by one or more groups R, where in each case one or more non-adjacent CH2 groups may be substituted by RC=CR, C≡C, Si(R) 2. Ge(R) 2 , Sn(R) 2 , C=O, C=S, C=Se, P(=O)(R), SO, SO 2 , O, S or CONR replacement and one or Multiple H atoms may be replaced by D, F, Cl, Br, I, CN or NO), aromatic or heteroaromatic ring systems with 5 to 60 aromatic ring atoms (which in each case may be replaced by a or more groups R substituted), and aryloxy groups having 5 to 60 aromatic ring atoms (which may be substituted by one or more groups R); the prerequisites are that R B1 to R B8 and RY are not represents D; and wherein two adjacent groups R A1 to R A8 , R B1 to R B8 , RY or R X can together form an aliphatic, aromatic or heteroaromatic ring system, which can be passed through one or more substituted by a group R; R at each occurrence identically or differently represents H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar) 2 , S(=O)Ar, S(=O) 2 Ar, N(R') 2 , N(Ar) 2 , NO 2 , Si(R') 3 , B(OR') 2 , OSO 2 R', Straight-chain alkyl, alkoxy or alkylthio having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 40 C atoms (each of which can be One or more groups R' are substituted, wherein in each case one or more non-adjacent CH 2 groups can be replaced by R'C=CR', C≡C, Si(R') 2 , Ge(R ') 2 , Sn(R') 2 , C=O, C=S, C=Se, P(=O)(R'), SO, SO 2 , O, S or CONR' substitution and one or more of them H atoms may be replaced by D, F, Cl, Br, I, CN or NO), aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms (which in each case may be replaced by one or a plurality of groups R'substituted), or an aryloxy group having 5 to 60 aromatic ring atoms (which may be substituted by one or more groups R'); where two adjacent substituents R may form together aliphatic or aromatic ring system, which may be substituted by one or more radicals R'; Ar is, at each occurrence, identical or different, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms , which in each case may also be substituted by one or more radicals R';R' at each occurrence identically or differently represents H, D, F, Cl, Br, I, CN, with 1 to 20 C-atom straight-chain alkyl, alkoxy or alkylthio or branched or cyclic alkyl, alkoxy or alkylthio having 3 to 20 C-atoms (wherein each case one or more Non-adjacent CH2 groups can be replaced by SO, SO2 , O, S and one or more H atoms can be replaced by D, F, Cl, Br or I), or have 5 to 24 aromatic rings Atoms of aromatic or heteroaromatic ring systems; and n at each occurrence, identically or differently, 0 or 1; wherein when n is 0, corresponding to the absence of Ar AS or Ar BS , and an anthracenyl direct bond bound to a group G1 or G2 ; m is 0 or 1; characterized in that the compound of formula (H1) contains at least one deuterium atom, and the compound of formula (H2) is substantially free of deuterium atoms. 根據請求項1之組成物，其中該基團G 1係選自下列式中之一者所示的基團：
Figure 03_image011
Figure 03_image013
Figure 03_image015
其中： X    在每次出現時相同或不同地代表C-R X或N；其先決條件為當X鍵結至基團Ant 1時，X代表C； E 1、E 2、E 3、E 4在每次出現時相同或不同地代表單鍵、-BR 0-、-C(R 0) 2-、-Si(R 0) 2-、-C(=O)-、-O-、-S-、 -S(=O)-、-SO 2-、-N(R 0)-或-P(R 0)-；其先決條件為基團E 1和E 3中只有一者可為單鍵，及基團E 4和E 2中只有一者可為單鍵； E 5代表-BR 0-、-C(R 0) 2-、-Si(R 0) 2-、-C(=O)-、-O-、-S-、-S(=O)-、-SO 2-、-N(R 0)-或-P(R 0)-； R 0在每次出現時相同或不同地代表H、D、F、CN、具有1至40個C原子之直鏈烷基或具有3至40個C原子之支鏈或環狀烷基(彼等各自可經一或多個基團R取代)、具有5至60個芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)；其中二個相鄰的取代基R 0可形成單環或多環的脂族環系統或芳族環系統，其可經一或多個基團R取代； R X、R具有與請求項1中相同的意義。 According to the composition of claim 1, wherein the group G is selected from the groups shown in one of the following formulas:
Figure 03_image011
Figure 03_image013
Figure 03_image015
wherein: X represents CR X or N identically or differently at each occurrence; the prerequisite is that when X is bonded to the group Ant 1 , X represents C; E 1 , E 2 , E 3 , E 4 in each The same or different occurrences represent a single bond, -BR 0 -, -C(R 0 ) 2 -, -Si(R 0 ) 2 -, -C(=O)-, -O-, -S-, -S(=O)-, -SO 2 -, -N(R 0 )- or -P(R 0 )-; with the prerequisite that only one of the radicals E 1 and E 3 may be a single bond, and Only one of the groups E 4 and E 2 may be a single bond; E 5 represents -BR 0 -, -C(R 0 ) 2 -, -Si(R 0 ) 2 -, -C(=O)-, -O-, -S-, -S(=O)-, -SO 2 -, -N(R 0 )- or -P(R 0 )-; R 0 represents H identically or differently at each occurrence , D, F, CN, straight chain alkyl having 1 to 40 C atoms or branched or cyclic alkyl having 3 to 40 C atoms (each of which may be substituted by one or more groups R) , an aromatic or heteroaromatic ring system (which in each case may be substituted by one or more groups R) having 5 to 60 aromatic ring atoms; wherein two adjacent substituents R can form a single Cyclic or polycyclic aliphatic ring system or aromatic ring system, which may be substituted by one or more groups R; R X , R have the same meanings as in Claim 1. 根據請求項1或2之組成物，其中式(H1)化合物係選自下列式之化合物：
Figure 03_image017
Figure 03_image019
Figure 03_image021
Figure 03_image023
其中該等符號具有與請求項1中相同的意義，及其中式(G1-1-1)至(G1-12-3)之化合物包含至少一個氘原子。 According to the composition of claim 1 or 2, wherein the compound of formula (H1) is selected from the compounds of the following formulae:
Figure 03_image017
Figure 03_image019
Figure 03_image021
Figure 03_image023
Wherein these symbols have the same meanings as in Claim 1, and wherein the compounds of formulas (G1-1-1) to (G1-12-3) contain at least one deuterium atom. 根據前述請求項中一或多項之組成物，其中式(H1)化合物之分子量為Mw≥350 g/mol。The composition according to one or more of the preceding claims, wherein the molecular weight of the compound of formula (H1) is Mw≥350 g/mol. 根據前述請求項中一或多項之組成物，其中，在式(H1)化合物中，該至少一個氘原子為基團Ant 1上或基團G1上的取代基。 The composition according to one or more of the preceding claims, wherein, in the compound of formula (H1), the at least one deuterium atom is a substituent on the group Ant1 or on the group G1. 根據前述請求項中一或多項之組成物，其中該式(H1)化合物係至少10%氘化，其意指式(H1)化合物中至少10% 的可用H原子被氘原子置換。The composition according to one or more of the preceding claims, wherein the compound of formula (H1) is at least 10% deuterated, which means that at least 10% of the available H atoms in the compound of formula (H1) are replaced by deuterium atoms. 根據前述請求項中一或多項之組成物，其中該式(H1)化合物係以等於或高於該組成物的1重量%之比例存在於該組成物中。The composition according to one or more of the preceding claims, wherein the compound of formula (H1) is present in the composition in a proportion equal to or higher than 1% by weight of the composition. 根據前述請求項中一或多項之組成物，其中基團G 2係選自下列式中之一者所示的基團：
Figure 03_image025
其中： Y    在每次出現時相同或不同地代表C-R Y或N；其先決條件為當Y鍵結至基團Ant 2時，Y代表C；及其中該等符號R Y和R 0具有與請求項1中相同的意義。 According to the composition of one or more of the preceding claims, wherein the group G2 is selected from the groups shown in one of the following formulae:
Figure 03_image025
wherein: Y represents CR Y or N identically or differently at each occurrence; it is a prerequisite that Y represents C when Y is bonded to the group Ant 2 ; and wherein the symbols RY and R 0 have the same Same meaning as in item 1. 根據前述請求項中一或多項之組成物，其中該式(H2)化合物係選自下列式之基團：
Figure 03_image027
其中該等符號具有與請求項1中相同的意義。 The composition according to one or more of the preceding claims, wherein the compound of formula (H2) is a group selected from the following formulae:
Figure 03_image027
Wherein these symbols have the same meanings as in Claim 1. 根據前述請求項中一或多項之組成物，其中該式(H2)化合物係以等於或高於該組成物的1重量%的比例存在於該組成物中。The composition according to one or more of the preceding claims, wherein the compound of formula (H2) is present in the composition in a proportion equal to or higher than 1% by weight of the composition. 根據前述請求項中一或多項之組成物，其中該等基團Ar A1和Ar B1在每次出現時係相同或不同地選自由下列所組成之群組：苯基、聯苯、聯三苯(terphenyl)、聯四苯(quaterphenyl)、茀、螺二茀、萘、蒽、菲、聯伸三苯(triphenylene)、丙二烯合茀(fluoranthene)、稠四苯、
Figure 111113012-001
(chrysene)、苯并蒽、苯并菲、芘或苝、二苯并呋喃、咔唑和二苯并噻吩，彼等各自可經一或多個基團R取代在任何自由位置；及其中Ar A1、Ar B1也可為上述基團中之二或更多者的組合。 The composition according to one or more of the preceding claims, wherein the groups Ar A1 and Ar B1 are identically or differently selected at each occurrence from the group consisting of: phenyl, biphenyl, terphenyl (terphenyl), bitetraphenyl (quaterphenyl), fennel, spirodipic, naphthalene, anthracene, phenanthrene, triphenylene, fluoranthene, condensed tetraphenyl,
Figure 111113012-001
(chrysene), benzanthracene, triphenylene, pyrene or perylene, dibenzofuran, carbazole and dibenzothiophene, each of which may be substituted at any free position by one or more groups R; and wherein Ar A1 and Ar B1 can also be a combination of two or more of the above groups. 根據前述請求項中一或多項之組成物，其中該摻雜劑材料為螢光發光體。The composition according to one or more of the preceding claims, wherein the dopant material is a fluorescent emitter. 根據前述請求項中一或多項之組成物，其中該摻雜劑材料為選自由下列所組成之群組的螢光發光體： - 含有三個直接鍵結至氮的經取代或未經取代之芳族或雜芳族環系統的芳基胺； - 橋聯三芳基胺； - 具有至少14個芳族環原子之縮合芳族或雜芳族環系統； - 茚并茀、茚并茀胺或茚并茀二胺； - 苯并茚并茀、苯并茚并茀胺或苯并茚并茀二胺； - 二苯并茚并茀、二苯并茚并茀胺或二苯并茚并茀二胺； - 含有具有至少10個芳族環原子的縮合芳基之茚并茀； - 雙茚并茚并茀； - 茚并二苯并呋喃；茚并茀胺或茚并茀二胺； - 茀二聚物； - 啡㗁𠯤；及 - 硼衍生物。 The composition according to one or more of the preceding claims, wherein the dopant material is a fluorescent emitter selected from the group consisting of: - arylamines containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen; - Bridged triarylamines; - condensed aromatic or heteroaromatic ring systems having at least 14 aromatic ring atoms; - indenoxene, indenoxamine or indenoxenediamine; - benzoindenoxene, benzoindenoxamine or benzoindenoxenediamine; - dibenzoindenofluorene, dibenzoindenotermineamine or dibenzoindenoterminediamine; - indenoxenes containing condensed aryl groups having at least 10 aromatic ring atoms; - Bisindenoindenofluorene; - Indenodibenzofuran; indenoxamine or indenoxenediamine; - Dimer of fennel; - coffee 㗁𠯤; and - Boron derivatives. 根據前述請求項中一或多項之組成物，其中該摻雜劑材料為式(E-1)、(E-2)、(E-3)或(E-4)之螢光發光體，
Figure 03_image029
其中 Ar 10、Ar 11、Ar 12在每次出現時相同或不同地為具有6至60個芳族環原子之芳族或雜芳族環系統，其在各情況下亦可經一或多個基團R取代；其先決條件為至少一個基團Ar 10、Ar 11、Ar 12為具有10至40個芳族環原子之芳族或雜芳族環系統且含有至少一個由2至4個彼此縮合的芳族環組成的縮合芳基或雜芳基，其中該芳族或雜芳族環系統可經一或多個基團R取代； R   具有與請求項1相同的定義；及 e    為1、2、3或4；更佳地，e為1；
Figure 03_image031
其中 Ar 20、Ar 21、Ar 22在每次出現時相同或不同地為具有6至30個芳族環原子之芳基或雜芳基，其在各情況下亦可經一或多個基團R取代； E 20在每次出現時係相同或不同地選自BR、C(R 0) 2、Si(R 0) 2、C=O、C=NR 0、C=C(R 0) 2、O、S、S=O、SO 2、NR 0、PR 0、P(=O)R 0或P(=S)R 0之基團；其中Ar 20、Ar 21和E 20一起形成五員環或六員環，及Ar 21、Ar 22和E 20一起形成五員環或六員環； R 0在每次出現時相同或不同地代表H、D、F、具有1至20個(較佳1至10個) C原子之直鏈烷基或具有3至20個(較佳為3至10個) C原子之支鏈或環狀烷基(彼等各自可經一或多個R基團取代，其中在各情況下一或多個非相鄰的CH 2基團可經O或S置換和其中一或多個H原子可經D或F置換)、或具有5至40個(較佳為5至30個，更佳為6至18個)芳族環原子之芳族或雜芳族環系統(其在各情況下可經一或多個基團R取代)，其中兩個相鄰的基團R 0可一起形成脂族或芳族環系統，其可經一或多個基團R取代， R   具有與請求項1中相同的定義； p、q   在每次出現時相同或不同地為0或1，其先決條件為p+q=1； r     為1、2或3；
Figure 03_image033
其中 Ar 30、Ar 31、Ar 32在每次出現時相同或不同地代表具有5至22個(較佳5至18個，更佳6至14個)芳族環原子之經取代或未經取代之芳基或雜芳基； E 30代表B或N； E 31、E 32、E 33在每次出現時相同或不同地代表O、S、C(R 0) 2、C=O、C=S、C=NR 0、C=C(R 0) 2、Si(R 0) 2、BR 0、NR 0、PR 0、SO 2、SeO 2或化學鍵，其先決條件為若E 30為B，則基團E 31、E 32、E 33中之至少一者代表NR 0，及若E 30為N，則基團E 31、E 32、E 33中之至少一者代表BR 0； R 0具有與上述相同的定義； s、t、u 在每次出現時相同或不同地為0或1，其先決條件為s+t+u≥1；
Figure 03_image035
其中 Ar 40、Ar 41、Ar 42在每次出現時相同或不同地代表具有5至22個(較佳5至18個，更佳6至14個)芳族環原子之經取代或未經取代之芳基或雜芳基； E 41、E 42、E 43在每次出現時相同或不同地代表O、S、C(R 0) 2、C=O、C=S、C=NR 0、C=C(R 0) 2、Si(R 0) 2、BR 0、NR 0、PR 0、SO 2、SeO 2或化學鍵，其先決條件為基團E 41、E 42、E 43中之至少一者存在且代表化學鍵； R 0具有與上述相同的定義； i、g、h 在每次出現時相同或不同地為0或1，其先決條件為i+g+h≥1。 The composition according to one or more of the preceding claims, wherein the dopant material is a fluorescent emitter of formula (E-1), (E-2), (E-3) or (E-4),
Figure 03_image029
wherein Ar 10 , Ar 11 , Ar 12 are identically or differently at each occurrence an aromatic or heteroaromatic ring system having 6 to 60 aromatic ring atoms, which may in each case also be replaced by one or more The group R is substituted; the prerequisite for this is that at least one of the groups Ar 10 , Ar 11 , Ar 12 is an aromatic or heteroaromatic ring system with 10 to 40 aromatic ring atoms and contains at least one of 2 to 4 A condensed aryl or heteroaryl group consisting of condensed aromatic rings, wherein the aromatic or heteroaromatic ring system may be substituted by one or more groups R; R has the same definition as in Claim 1; and e is 1 , 2, 3 or 4; more preferably, e is 1;
Figure 03_image031
wherein Ar 20 , Ar 21 , Ar 22 are identically or differently at each occurrence an aryl or heteroaryl group having 6 to 30 aromatic ring atoms, which in each case may also be represented by one or more groups R substitution; E 20 at each occurrence is identically or differently selected from BR, C(R 0 ) 2 , Si(R 0 ) 2 , C=O, C=NR 0 , C=C(R 0 ) 2 , O, S, S=O, SO 2 , NR 0 , PR 0 , P(=O)R 0 or P(=S)R 0 groups; where Ar 20 , Ar 21 and E 20 together form five members ring or a six-membered ring, and Ar 21 , Ar 22 and E 20 together form a five-membered ring or a six-membered ring; R 0 represents H, D, F, with 1 to 20 (compared to Preferably 1 to 10) straight-chain alkyl groups of C atoms or branched or cyclic alkyl groups having 3 to 20 (preferably 3 to 10) C atoms (each of them can be modified by one or more R groups group substitution, where in each case one or more non-adjacent CH groups can be replaced by O or S and where one or more H atoms can be replaced by D or F), or with 5 to 40 (compared preferably 5 to 30, more preferably 6 to 18) aromatic or heteroaromatic ring systems (which in each case may be substituted by one or more radicals R) of aromatic ring atoms, wherein two phases The adjacent radicals R 0 may together form an aliphatic or aromatic ring system, which may be substituted by one or more radicals R, R having the same definition as in claim 1; p, q in each occurrence are the same or is variously 0 or 1, the prerequisite for which is p+q=1; r is 1, 2 or 3;
Figure 03_image033
Wherein Ar 30 , Ar 31 , Ar 32 represent identically or differently each occurrence of substituted or unsubstituted aromatic ring atoms having 5 to 22 (preferably 5 to 18, more preferably 6 to 14) aromatic ring atoms. aryl or heteroaryl; E 30 represents B or N; E 31 , E 32 , E 33 represent O, S, C(R 0 ) 2 , C=O, C= S, C=NR 0 , C=C(R 0 ) 2 , Si(R 0 ) 2 , BR 0 , NR 0 , PR 0 , SO 2 , SeO 2 or a chemical bond, the prerequisite is that if E 30 is B, Then at least one of the groups E 31 , E 32 , E 33 represents NR 0 , and if E 30 is N, at least one of the groups E 31 , E 32 , E 33 represents BR 0 ; R 0 has same definition as above; s, t, u are identically or differently 0 or 1 at each occurrence, with the precondition that s+t+u≥1;
Figure 03_image035
Wherein Ar 40 , Ar 41 , Ar 42 represent identically or differently each occurrence of substituted or unsubstituted aromatic ring atoms having 5 to 22 (preferably 5 to 18, more preferably 6 to 14) aromatic ring atoms. Aryl or heteroaryl; E 41 , E 42 , E 43 represent O, S, C(R 0 ) 2 , C=O, C=S, C=NR 0 , C=C(R 0 ) 2 , Si(R 0 ) 2 , BR 0 , NR 0 , PR 0 , SO 2 , SeO 2 or a chemical bond, the prerequisite being at least one of the groups E 41 , E 42 , E 43 One is present and represents a chemical bond; R 0 has the same definition as above; i, g, h are identically or differently 0 or 1 at each occurrence, with the prerequisite that i+g+h≧1. 一種調配物，其包含根據請求項1至14中任一或多項之組成物和至少一種溶劑。A formulation comprising the composition according to any one or more of claims 1 to 14 and at least one solvent. 一種製造電子裝置之方法，該電子裝置包含至少一層包含根據請求項1至14中一或多項之組成物的層，該方法包括： a) 製備一種包含至根據請求項1至14中一或多項之組成物和至少一種溶劑的調配物； b) 將步驟a)中製備的調配物施加在基板上或另一層上以形成一層； c) 將該層乾燥以移除該溶劑。 A method of manufacturing an electronic device comprising at least one layer comprising a composition according to one or more of claims 1 to 14, the method comprising: a) preparing a formulation comprising one or more of the compositions according to claims 1 to 14 and at least one solvent; b) applying the formulation prepared in step a) to a substrate or another layer to form a layer; c) drying the layer to remove the solvent. 根據請求項16之方法，其中該調配物係以塗佈法或印刷法施加。The method according to claim 16, wherein the formulation is applied by coating or printing. 根據請求項16或17之方法，其中該調配物係以泛塗(flood coating)、浸塗、噴塗、旋轉塗佈、網版印刷、凸版印刷、凹版印刷、輥塗、噴墨印刷、旋轉印刷、快乾印刷(flexographic printing)、平版印刷、縫模塗佈(slot die coating)或噴嘴印刷施加。The method according to claim 16 or 17, wherein the formulation is applied by flood coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, roll coating, inkjet printing, rotary printing , flexographic printing, lithographic printing, slot die coating or nozzle printing application. 一種有機電致發光裝置，其包含： 陽極； 陰極； 至少一個介於陽極和陰極之間的發光層，其中該介於陽極和陰極之間的發光層包含如請求項1至14中所定義之組成物。 An organic electroluminescent device comprising: anode; cathode; At least one light-emitting layer between the anode and the cathode, wherein the light-emitting layer between the anode and the cathode comprises the composition as defined in claims 1 to 14. 一種根據請求項19之有機電致發光裝置，其中該發光層不包含磷光發光體作為摻雜劑材料。An organic electroluminescent device according to claim 19, wherein the emitting layer does not contain a phosphorescent emitter as a dopant material.
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