CN109715640B - 用于oled用途的钨(vi)络合物 - Google Patents
用于oled用途的钨(vi)络合物 Download PDFInfo
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- CN109715640B CN109715640B CN201780049687.XA CN201780049687A CN109715640B CN 109715640 B CN109715640 B CN 109715640B CN 201780049687 A CN201780049687 A CN 201780049687A CN 109715640 B CN109715640 B CN 109715640B
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- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical class [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 title abstract description 19
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- 239000002019 doping agent Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 135
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 76
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 62
- 239000007787 solid Substances 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
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- 239000003446 ligand Substances 0.000 description 29
- 239000011541 reaction mixture Substances 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000010992 reflux Methods 0.000 description 24
- -1 tungsten (VI) ions Chemical class 0.000 description 24
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- 125000003118 aryl group Chemical group 0.000 description 22
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- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
具有结构I的络合物的OLED发射体。所述络合物具有钨(VI)中心和两个配位单元，所述配位单元是独立的或连接在一起。每个配位单元用氮‑钨键和氧‑钨键配位到中心。所述钨(VI)发射体可用于发光器件。
Description
技术领域
本文描述了钨(VI)发射体及其在有机发光二极管（OLED）中的用途。
背景
有机发光二极管（OLED）是具有许多实际用途的创新技术。由于高图像质量，为高端消费类电子产品如智能手机配备超薄和可固定的OLED。如今，市场上的大多数有源矩阵（AM）OLED使用基于铱的材料作为发射体。由于磷光OLED将所有单重态和三重态能量电能转化成光能，其是适用于照明的节能技术。但是，降低将这一技术转化成低端产品的成本是一个巨大的挑战。磷光OLED中的昂贵零件之一是磷光发射体。需要贵金属如铱、金或铂引发系间窜越以获得磷光。
钨，作为地球上相对丰富的金属，比铱和铂便宜。自从发明白炽灯泡以来，使用钨已成为惯例。在广泛使用超过100年后也没有报道对人类或环境的负面影响。由于钨是具有比得上铱和铂（Ir和Pt的自旋轨道耦合常数分别 = 3909和4481 cm-1）的自旋轨道耦合常数（2433 cm-1）的第三行过渡金属，其因此应具有促进系间窜越和磷光的强重原子效应。此外，在钨(VI)离子的被占轨道中没有可用d电子，在发射性MLCT激发态中常遇到的失活d-d配体场激发态不存在并且不会促成非放射衰变，因此重要的是，设计具有高发射能量的钨(VI)络合物（例如蓝色发射体），其中有问题的d-d激发态在能量上接近。但是，在文献中没有报道强发射性钨(VI)络合物。
概述
本文描述了具有结构I的化学结构的新型钨(VI)发射体，及其在有机发光二极管（OLED）中的用途。在一个实施方案中，结构I的基于钨(VI)的化合物如下所示：
结构I
其中W是具有VI氧化态的钨中心。R1和R2是用氮-钨键和氧-钨键配位到钨(VI)中心的配位单元。R3是连接R1和R2的连接体，其可含有额外原子或仅是单键。在一些情况下，R3可不存在，其中R1和R2是两个独立的双齿配体。在另一实施方案中，R1和R2独立地为芳族配位单元。
本文还提供由结构I的钨(VI)发射体制成的器件。
附图简述
图301: 发射体1013的透视图。
图302: 发射体1017的透视图。
图303: 发射体1018的透视图。
图304: 发射体1027的透视图。
图305: 发射体1012的HOMO和LUMO的图。
图306: 发射体1015的HOMO和LUMO的图。
图307: 发射体1027的HOMO和LUMO的图。
图308: 用发射体1015制成的器件的EL谱。
图309: 用发射体1015制成的器件的EQE-亮度关系。
图310: 发射体1031的x-射线晶体结构的透视图。
图311: 发射体1034的x-射线晶体结构的透视图。
详述
定义
为了利于理解本文中公开的主题，下面定义如本文中所用的许多术语、缩写或其它速记记录文字。没有定义的任何术语、缩写或速记记录文字被理解为具有技术人员在本申请提交时使用的普通含义。
“氨基”是指可任选取代的伯、仲或叔胺。尤其包括作为杂环的成员的仲或叔胺氮原子。还尤其包括例如被酰基基团取代的仲或叔氨基。氨基的一些非限制性实例包括–NR’R”，其中R’和R”各自独立地为H、烷基、芳基、芳烷基、烷芳基、环烷基、酰基、杂烷基、杂芳基或杂环基。
“烷基”是指含有碳和氢并可以是支链或直链的完全饱和无环一价基团。烷基的实例包括但不限于具有1-20、1-10或1-6个碳原子的烷基、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正庚基、正己基、正辛基和正癸基。
“烷基氨基”是指基团-NHR或–NR2，其中各R独立地为烷基。烷基氨基的代表性实例包括但不限于甲基氨基、(1-甲基乙基)氨基、甲基氨基、二甲基氨基、甲基乙基氨基和二(1-甲基乙基)氨基。
术语“羟烷基”是指被一个或多个，优选一个、两个或三个羟基取代的如本文中定义的烷基。羟烷基的代表性实例包括但不限于羟甲基、2-羟乙基、2-羟丙基、3-羟丙基、1-(羟甲基)-2-甲基丙基、2-羟丁基、3-羟丁基、4-羟丁基、2,3-二羟丙基、2-羟基-1-羟甲基乙基、2,3-二羟丁基、3,4-二羟丁基和2-(羟甲基)-3-羟基-丙基，优选2-羟乙基、2,3-二羟丙基和1-(羟甲基)2-羟乙基。
本文所用的术语“烷氧基”是指基团–ORx，其中Rx是烷基。示例性的烷氧基包括但不限于甲氧基、乙氧基和丙氧基。
“芳族”或“芳基”是指芳基或杂芳基。
“芳基”是指任选取代的碳环芳基（例如具有6-20个碳原子）。在一些实施方案中，芳基包括苯基、联苯、萘基、取代的苯基、取代的联苯或取代的萘基。在其它实施方案中，芳基是苯基或取代的苯基。
“芳烷基”是指被芳基取代的烷基。芳烷基的一些非限制性实例包括苄基和苯乙基。
“酰基”是指式−C(=O)H、−C(=O)−烷基、−C(=O)−芳基、−C(=O)−芳烷基或−C(=O)−烷芳基的一价基团。
“卤素”是指氟、氯、溴和碘。
“苯乙烯基”是指衍生自苯乙烯的一价基团C6H5-CH=CH-。
本文中用于描述化合物或化学基团的“取代的”是指该化合物或化学基团的至少一个氢原子被第二个化学基团替代。取代基的非限制性实例是在本文中公开的示例性化合物和实施方案中发现的那些，以及卤素；烷基；杂烷基；烯基；炔基；芳基；杂芳基；羟基；烷氧基；氨基；硝基；巯基；硫醚；亚胺；氰基；酰氨基；phosphonato；膦；羧基；硫代羰基；磺酰基；磺酰胺；酮；醛；酯；氧代；卤代烷基（例如三氟甲基）；碳环环烷基，其可以是单环或稠合或非稠合多环（例如环丙基、环丁基、环戊基或环己基），或杂环烷基，其可以是单环或稠合或非稠合多环（例如吡咯烷基、哌啶基、哌嗪基、吗啉基或噻嗪基）；碳环或杂环的、单环或稠合或非稠合多环芳基（例如苯基、萘基、吡咯基、吲哚基、呋喃基、噻吩基、咪唑基、噁唑基、异噁唑基、噻唑基、三唑基、四唑基、吡唑基、吡啶基、喹啉基、异喹啉基、吖啶基、吡嗪基、哒嗪基、嘧啶基、苯并咪唑基、苯并噻吩基或苯并呋喃基）；氨基（伯、仲或叔）；邻低级烷基；邻芳基、芳基；芳基-低级烷基；−CO2CH3；−CONH2；−OCH2CONH2；−NH2；−SO2NH2；−OCHF2；−CF3；−OCF3；–NH(烷基)；–N(烷基)2；–NH(芳基)；–N(烷基)(芳基)；–N(芳基)2；–CHO；–CO(烷基)；−CO(芳基)；−CO2(烷基)；和–CO2(芳基)；且此类基团也可任选被稠环结构或桥，例如−OCH2O−取代。这些取代基可任选被选自此类基团的取代基进一步取代。除非另行规定，否则本文中公开的所有化学基团都可被取代。例如，本文所述的“取代的”烷基、烯基、炔基、芳基、烃基或杂环基团是被烃基基团、取代的烃基基团、杂原子或杂环取代的基团。此外，取代基可包括其中碳原子被杂原子如氮、氧、硅、磷、硼、硫或卤素原子取代的基团。这些取代基可包括卤素、杂环、烷氧基、烯氧基、炔氧基、芳氧基、羟基、受保护的羟基、酮基、酰基、酰氧基、硝基、氨基、酰氨基、氰基、巯基、缩酮、缩醛、酯和醚。
在一个方面中，“连接体”包含二价连接基团。该二价连接基团包括但不限于-O-、-S-、亚烷基（例如具有1至6个碳原子）、亚环烷基（例如具有3至12个碳原子）、亚烯基（例如具有2至8个碳原子）、亚芳基、磺酰基、羰基、-CH(OH)-、-C(=O)O-、-O-C(=O)-或heterocyclene基团或两个或更多个此类基团的组合。这些基团各自可被一个或多个取代基取代。更具体的实例包括亚甲基、亚乙基、亚丙基、亚环丙基、亚环丁基、亚环戊基、亚环己基、-CH2CH(OH)CH2-O-CH2-基团，它们都可被进一步取代。
在一个方面中，本发明提供钨(VI)发射体。在一个实施方案中，提供结构I所示的有机金属发射体。结构I中的钨中心为+6氧化态并具有八面体几何。钨中心的配位点被四齿配体或两个双齿配体和两个氧原子占据。
钨(VI)发射体
在一个实施方案中，钨(VI)发射体具有结构II的化学结构：
结构II
其中R4–R13独立地为氢、卤素、羟基、未取代的烷基、取代的烷基、环烷基、未取代的芳基、取代的芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰氨基、芳烷基、氰基、羧基、硫基、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基。R4–R13的每对相邻R基团可独立地形成在结构II中所示的苯基环中具有2或4个碳原子的5-8元环。
在另一实施方案中，钨(VI)发射体具有结构III的化学结构：
结构III
其中R14–R25独立地为氢、卤素、羟基、未取代的烷基、取代的烷基、环烷基、未取代的芳基、取代的芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰氨基、芳烷基、氰基、羧基、硫基、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基。R14–R25的每对相邻R基团可独立地形成在结构III中所示的苯基环中具有2或4个碳原子的5-8元环。
在一个实施方案中，R4–R25独立地为氢、卤素、羟基、含有1至10个碳原子的未取代的烷基、含有1至20个碳原子的取代的烷基、含有4至20个碳原子的环烷基、含有6至20个碳原子的未取代的芳基、含有6至20个碳原子的取代的芳基、含有1至20个碳原子的酰基、含有1至20个碳原子的烷氧基、含有1至20个碳原子的酰氧基、氨基、硝基、含有1至20个碳原子的酰氨基、含有1至20个碳原子的芳烷基、氰基、含有1至20个碳原子的羧基、巯基、苯乙烯基、含有1至20个碳原子的氨基羰基、含有1至20个碳原子的氨基甲酰基、含有1至20个碳原子的芳氧基羰基、含有1至20个碳原子的苯氧基羰基或含有1至20个碳原子的烷氧基羰基。
根据结构I的钨(VI)发射体的某些具体的非限制性实例如下所示：
根据结构I的钨(VI)发射体的另一些非限制性实例如下所示：
钨(VI)发射体的制备
在一个实施方案中，具有结构I的化学结构的钨(VI)发射体可通过使相应配体与钨盐在合适的溶剂存在下和在合适的条件下反应制备。
实施例:
下面是例示实施本发明的实施方案的实施例。这些实施例不应被解释为限制。除非另行指明，否则所有百分比按重量计，且所有溶剂混合物比例按体积计。
实施例201 –发射体1012
向配体（56毫克，0.17毫摩尔）在干燥甲苯中的脱气溶液中加入WO2Cl2（50毫克，0.17毫摩尔）和吡啶（0.029毫升，0.37毫摩尔）。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷（10毫升）中。将二乙醚（30毫升）添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚（5x10毫升）洗涤。过滤该黄色固体并在真空下干燥。收率: 31%。1H NMR (500 MHz, CDCl3)δ = 8.41 (s, 1H), 8.36 (d, J = 1.9, 1H), 7.64 – 7.57 (m, 1H), 7.50 (ddd, J = 8.7, 7.0, 1.8, 1H), 7.44 (d, J = 7.8, 2H), 7.20 (d, J = 8.3, 1H), 7.09 – 7.03(m, 1H), 6.98 (d, J = 8.5, 1H), 6.80 (t, J = 7.5, 1H), 4.55 (t, J = 11.0,1H), 2.89 (t, J = 10.5, 1H), 2.56 (d, J = 15.4, 1H), 2.42 (d, J = 10.0, 1H),2.09 (d, J = 14.5, 2H), 1.84 – 1.65 (m, 2H), 1.48 – 1.35 (m, 2H)。13C NMR (151MHz, CD2Cl2) δ = 168.11, 163.72, 162.26, 158.90, 138.54, 136.28, 135.44,133.51, 124.87, 122.18, 122.10, 121.41, 120.92, 118.55, 74.55, 72.06, 30.70,29.24, 25.11, 24.35。IR (KBr盘, v/cm-1): 935 (m, W=O), 892 (m, W=O)。FAB-MS (+ve, m/z): 537.5 [M+]. C20H20N2O4W的分析计算值: C, 44.80；H, 3.76；N, 5.22；实测值:C, 44.71；H, 4.15；N, 5.26。
实施例202 - 发射体1013的合成
向配体（0.19克，0.35毫摩尔）在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 42%。1H NMR (500 MHz,CDCl3) δ = 8.43 – 8.39 (m, 1H), 8.36 (d, J = 2.0, 1H), 7.73 (d, J = 2.5, 1H),7.60 (d, J = 2.6, 1H), 7.34 (d, J = 2.5, 1H), 7.30 (d, J = 2.5, 1H), 4.49(dd, J = 10.7, 2.7, 1H), 2.84 (t, J = 9.7, 1H), 2.52 (dd, J = 12.1, 3.1, 1H),2.40 (d, J = 11.6, 1H), 2.06 (s, 2H), 1.80 – 1.66 (m, 2H), 1.66 – 1.54 (m,2H), 1.48 (s, 9H), 1.36 (s, 9H), 1.32 (s, 9H), 1.27 (s, 9H)。13C NMR (126 MHz,CDCl3) δ = 165.01, 163.10, 162.63, 155.90, 143.48, 140.54, 139.64, 139.38,132.64, 130.68, 129.49, 126.29, 123.78, 121.63, 73.31, 71.60, 53.61, 53.39,53.18, 52.96, 35.33, 34.25, 33.98, 31.09, 30.89, 30.33, 29.84, 29.38, 28.57,24.63, 23.87, 22.31。IR (KBr盘, v/cm-1): 939 (m, W=O), 894 (m, W=O)。FAB-MS (+ve, m/z): 762.0 [M+]。C36H52N2O4W的分析计算值: C, 44.80；H, 3.76；N, 5.22；实测值:C, 44.71；H, 4.15；N, 5.26。
实施例203 - 发射体1014的合成
向配体（0.44克，0.70毫摩尔）在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 12%。1H NMR (500 MHz,CDCl3) δ = 8.39 (s, 1H), 8.33 (d, J = 0.7, 1H), 8.05 (d, J = 1.8, 1H), 7.91(d, J = 2.8, 1H), 7.63 (d, J = 1.8, 2H), 4.68 – 4.52 (m, 1H), 3.06 – 2.92 (m,1H), 2.54 (d, J = 14.8, 1H), 2.42 (d, J = 10.5, 1H), 2.10 (dd, J = 14.3, 2.5,1H), 1.72 (m, 3H), 1.47 (s, 2H)。IR (KBr disk, v/cm
1): 939 (m, W=O), 899 (m,W=O)。FAB-MS (+ve, m/z): 852.7 [M+]。C20H16Br4N2O4W的分析计算值: C, 28.20；H, 1.89；N, 3.29；实测值: C, 28.38；H, 1.99；N, 3.31。
实施例204 - 发射体1015的合成
向配体在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 57%。1H NMR (500 MHz, CDCl3) δ = 8.33 (s,1H), 8.14 (s, 1H), 7.55 (td, J = 7.0, 1.7 Hz, 1H), 7.43 (td, J = 6.9, 1.7 Hz,1H), 7.37 (dd, J = 7.7, 1.6 Hz, 1H), 7.31 (dd, J = 8.2, 1.6 Hz, 1H), 7.11 (d,J = 8.3 Hz, 1H), 7.02 (td, J = 7.6, 0.8 Hz, 1H), 6.74 (m, 2H), 5.01 (m, 1H),4.19 (m, 2H), 3.84 (m, 1H), 2.54 (m, 1H), 2.05 (m, 1H)。13C NMR (151 MHz,CDCl3) δ = 169.15, 167.79, 162.99, 159.88, 138.16, 135.20, 133.53, 133.29,122.55, 122.31, 121.20, 121.16, 120.56, 118.24, 64.69, 59.88, 30.66。FAB-MS (+ve, m/z): 496.9 [MH+]。C17H16N2O4W•0.25 CH2Cl2的分析计算值: C, 40.04；H, 3.21；N,5.41；实测值: C, 40.11；H, 3.35；N, 5.52。
实施例205 - 发射体1016的合成
向配体在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 82%。1H NMR (500 MHz, CDCl3) δ 8.30 (s, 1H),8.09 (s, 1H), 7.62 (d, J = 2.4 Hz, 1H), 7.50 (d, J = 2.4 Hz, 1H), 7.19 (d, J= 2.4 Hz, 1H), 7.10 (d, J = 2.4 Hz, 1H), 5.03 (m, 1H), 4.13 (m, 2H), 3.79 (m,1H), 2.50 (m, 1H), 1.99 (m, 1H), 1.44 (s, 9H), 1.32 (s, 9H), 1.26 (s, 9H),1.05 (s, 9H)。13C NMR (151 MHz, CDCl3) δ = 169.06, 165.28, 163.47, 156.46,142.93, 140.23, 139.88, 139.49, 133.10, 130.25, 128.09, 126.83, 122.54,122.01, 64.22, 59.77, 35.41, 34.77, 34.30, 34.00, 31.43, 31.14, 31.01, 30.01,29.51。FAB-MS (+ve, m/z): 721.0 [MH+]。C33H48N2O4W•0.5CH2Cl2的分析计算值: C,52.73；H, 6.47；N, 3.67；实测值: C, 52.20；H, 6.50；N, 3.57。
实施例206 - 发射体1017的合成
向配体在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 45%。1H NMR (500 MHz, CDCl3) δ 8.27 (s, 1H),8.06 (s, 1H), 7.63 (dd, J = 8.8, 2.5 Hz, 1H), 7.49(d, J = 2.5 Hz, 1H), 7.47(dd, J = 8.8, 2.5 Hz, 1H), 7.42 (d, J = 2.5 Hz, 1H), 7.01 (d, J = 8.8 Hz,1H), 6.61 (d, J = 9.0 Hz, 1H), 4.98 (m, 1H), 4.32 (t, J = 10.5 Hz, 1H), 4.21(m, 1H), 3.83 (m, 1H), 2.53 (m, 1H), 2.03 (m, 1H)。13C NMR (151 MHz, CDCl3) δ =168.16, 166.75, 161.96, 158.85, 140.78, 137.85, 135.39, 134.62, 124.07,123.53, 123.16, 122.52, 112.91, 109.59, 65.35, 60.30, 31.12。FAB-MS (+ve, m/z): 654.5 [MH+]。C17H14Br2N2O4W•0.5CH2Cl2的分析计算值: C, 30.18；H, 2.17；N, 4.02；实测值: C, 30.13；H, 2.33；N, 4.03。
实施例207 - 发射体1018的合成
向配体在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 47%。1H NMR (500 MHz, CDCl3) δ 8.27 (s, 1H),8.06 (s, 1H), 7.49 (dd, J = 8.8, 2.6 Hz, 1H), 7.35 (dd, J = 9.5, 2.5 Hz, 1H),7.34(d, J = 2.5 Hz, 1H), 7.27(m, 1H), 7.06 (d, J = 8.8 Hz, 1H), 6.66 (d, J =9.1 Hz, 1H), 4.99 (m, 1H), 4.32 (t, J = 10.3 Hz, 1H), 4.21 (dt, J = 10.9, 5.4Hz, 1H), 3.83 (m, 1H), 2.53 (m, 1H), 2.03 (m, 1H)。13C NMR (151 MHz, CDCl3) δ168.27, 166.43, 162.04, 158.41, 138.17, 135.00, 132.35, 131.43, 125.90,123.47, 122.80, 122.71, 122.15, 118.58, 65.31, 60.29, 31.10。FAB-MS (+ve, m/z): 565.7 [MH+]。C17H14Cl2N2O4W•0.5CH2Cl2的分析计算值: C, 34.60；H, 2.49；N, 4.61；实测值: C, 34.47；H, 2.58；N, 4.52。
实施例208 - 发射体1019的合成
向配体在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 42%。1H NMR (400 MHz, CDCl3) δ = 8.28 (s,1H), 8.07 (s, 1H), 7.30–7.24 (m, 1H), 7.19 (ddd, J = 9.2, 8.1, 3.2, 1H), 7.07(m, 2H), 6.97 (dd, J = 8.1, 3.2, 1H), 6.68 (dd, J = 9.3, 4.5, 1H), 5.01 (m,1H), 4.30 (m, 1H), 4.21 (m, 1H), 3.84 (m, 1H), 2.52 (m, 1H), 2.05 (m, 1H)。13CNMR (151 MHz, CDCl3) δ 168.32, 164.53, 162.04, 157.38, 156.16, 155.79,155.36, 153.78, 126.60, 126.45, 122.55, 122.50, 122.37, 122,22, 121.95,121.90, 121.22, 121.16, 118.22, 118.06, 116.33, 116.18, 65.05, 60.17, 30.97(由于重叠，两个未解析)。19F NMR (376 MHz, CDCl3) δ -122.31, -125.89。FAB-MS (+ve,m/z): 532.9 [MH+]。C17H14F2N2O4W•1.5 CH2Cl2的分析计算值: C, 33.69；H, 2.60；N,4.25；实测值: C, 34.05；H, 2.63；N, 4.41。
实施例209 - 发射体1020的合成
向配体（0.34克，0.41毫摩尔）在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 51%。1H NMR (500 MHz,CD2Cl2) δ = 8.47 (s, 1H), 8.44 (d, J = 1.6, 1H), 7.84 – 7.80 (m, 1H), 7.69 (d,J = 7.5, 1H), 7.52 (s, 1H), 7.46 – 7.38 (m, 6H), 7.38 – 7.36 (m, 1H), 7.36 –7.29 (m, 2H), 7.22 (s, 1H), 4.58 – 4.48 (m, 1H), 2.98 (t, J = 10.7, 1H), 2.61(d, J = 11.2, 1H), 2.45 (d, J = 11.6, 1H), 2.09 (s, 2H), 2.00 (dd, J = 17.0,8.9, 6H), 1.95 – 1.84 (m, 3H), 1.79 (dd, J = 24.1, 12.2, 2H), 1.63 (dd, J = 26.2, 13.3, 4H), 1.52 – 1.40 (m, 2H), 1.09 (m, 24H), 0.82 – 0.67 (m, 12H)。13CNMR (126 MHz, CD2Cl2) δ = 168.55, 163.30, 162.14, 159.10, 153.64, 153.21,152.34, 149.62, 144.10, 140.88, 140.21, 140.19, 129.91, 129.61, 129.03,127.75, 127.63, 126.99, 123.87, 123.80, 123.70, 123.57, 122.07, 121.82,120.74, 111.47, 111.35, 110.20, 74.74, 72.19, 55.30, 54.70, 41.67, 41.17,41.13, 40.95, 40.71, 32.16, 32.14, 31.85, 30.85, 30.37, 30.31, 30.23, 30.07,29.39, 25.29, 24.74, 24.56, 24.44, 24.38, 24.25, 23.22, 23.17, 23.12, 23.02,14.35, 14.23。IR (KBr盘, v/cm-1): 937 (m, W=O), 891 (m, W=O)。FAB-MS (+ve, m/z):1049.5 [M+]。C58H76N2O4W•CHCl3的分析计算值: C, 60.65；H, 6.64；N, 2.40；实测值: C,60.10；H, 6.96；N, 2.58。
实施例210 - 发射体1021的合成
向配体（0.34克，0.41毫摩尔）在干燥甲苯中的脱气溶液中加入WO2Cl2和吡啶。该反应混合物在N2气氛下回流24小时。该反应混合物经硅藻土过滤并收集滤液。然后减压除去溶剂并将黄色残留物溶解在二氯甲烷中。将二乙醚添加到二氯甲烷溶液中导致黄色固体沉淀，其用二乙醚洗涤。过滤该黄色固体并在真空下干燥。收率: 70%。1H NMR (500 MHz,CDCl3) δ 8.35 (s, 1H), 8.19 (s, 1H), 7.81–7.75 (m, 1H), 7.55 (d, J = 7.6 Hz,1H), 7.45 (s, 1H), 7.42–7.29 (m, 4H), 7.27 (m, 2H), 7.22 (m, 1H), 7.19 (s,1H), 6.98 (s, 1H), 5.04 (m, 1H), 4.31 (t, J = 10.1 Hz, 1H), 4.21 (m, 1H),3.90 (m, 1H), 2.54 (m, 1H), 2.13–1.79 (m, 9H), 1.07 (m, 8H), 0.75–0.50 (m,20H)。13C NMR (151 MHz, CDCl3) δ = 168.60, 167.99, 163.05, 159.96, 152.89,152.32, 152.05, 148.41, 142.96, 140.38, 139.89, 139.50, 129.33, 128.79,127.17, 127.00, 126.93, 126.45, 122.95, 121.56, 121.39, 121.27, 111.39,111.14, 65.05, 60.28, 54.50, 54.00, 40.96, 40.58, 40.34, 40.17, 31.35, 26.09,26.00, 23.09, 13.95, 13.87, 13.84, 13.77 (由于靠近的化学位移，在芳族区中两个未解析)。FAB-MS (+ve, m/z): 897.0 [MH+]。C47H56N2O4W•1.5CH2Cl2的分析计算值: C,56.88；H, 5.81；N, 2.74；实测值: C, 56.31；H, 6.24；N, 2.88。
实施例211 - 发射体1023的合成
配体（0.15克，0.49毫摩尔）和WO2(acac)2（0.10, 0.24毫摩尔）在干燥甲醇中的混合物在N2下回流12小时并形成浅黄色固体。过滤该浅黄色固体并用甲醇洗涤。最后，产物从二氯甲烷-甲醇中重结晶提供浅黄色固体。收率: 60%。1H NMR (400 MHz, CDCl3) δ = 8.63(dd, J = 4.8, 1.1, 2H), 8.53 (dd, J = 8.5, 1.2, 2H), 8.11 (s, 2H), 7.60 (dd,J = 8.5, 4.8, 2H)。13C NMR (101 MHz, CDCl3) δ = 148.50, 139.66, 138.11, 135.92,127.97, 123.79, 111.04, 110.66。IR (KBr盘, v/cm-1): 947 (s, W=O), 915 (vs, W=O)。FAB-MS (+ve, m/z): 821.2 [M+]。C18H8Br4N2O4W的分析计算值: C, 26.37；H, 0.98；N,3.42；实测值: C, 26.52；H, 1.00；N, 3.57。
实施例212 - 发射体1024的合成
配体（0.17克，0.99毫摩尔）和WO2(acac)2在干燥甲醇中的混合物在N2下回流12小时并形成浅黄色固体。过滤该浅黄色固体并用甲醇洗涤。最后，产物从二氯甲烷-甲醇中重结晶提供浅黄色固体。收率: 63%。1H NMR (300 MHz, CDCl3) δ = 8.49 (dd, J = 4.8,1.3, 2H), 8.26 (dd, J = 8.4, 1.4, 2H), 7.39 – 7.27 (m, 4H), 2.63 (s, 6H),2.54 (s, 6H)。13C NMR (101 MHz, CDCl3) δ = 146.21, 139.83, 136.04, 132.67,127.18, 125.70, 125.12, 120.95, 17.24, 15.98。IR (KBr盘, v/cm-1): 944 (m, W=O),901 (m, W=O)。ESI-MS (+ve, m/z): 561.3 [M+]。C22H20N2O4W的分析计算值: C, 47.16；H,3.60；N, 5.00；实测值: C, 46.91；H, 3.78；N, 5.15。
实施例213 - 发射体1025的合成
配体（0.18克，0.62毫摩尔）和WO2(acac)2在干燥甲醇中的混合物在N2下回流12小时并形成浅黄色固体。过滤该浅黄色固体并用甲醇洗涤。最后，产物从二氯甲烷-甲醇中重结晶提供浅黄色固体。收率: 21%。1H NMR (500 MHz, CDCl3) δ = 8.62 (dd, J = 4.8,1.3, 1H), 8.35 (dd, J = 8.5, 1.4, 1H), 8.11 (dd, J = 8.3, 1.1, 2H), 7.89 (s,1H), 7.58 (t, J = 7.8, 2H), 7.52 – 7.46 (m, 2H), 7.44 (ddd, J = 6.0, 5.3,2.8, 4H), 7.36 (dd, J = 8.5, 4.8, 1H)。13C NMR (126 MHz, CDCl3) δ = 155.09,147.33, 140.69, 137.97, 137.91, 136.17, 132.11, 131.50, 129.95, 129.61,128.77, 128.12, 127.90, 127.82, 127.25, 122.32。IR (KBr盘, v/cm-1): 949 (m, W=O), 917 (m, W=O)。FAB-MS (+ve, m/z): 809.6 [M+]。C42H28N2O4W•1.5MeOH的分析计算值:C, 60.99；H, 4.00；N, 3.27；实测值: C, 60.92；H, 3.69；N, 3.42。
实施例214 – 发射体1026的合成
配体（0.21克，0.64毫摩尔）和WO2(acac)2在干燥甲醇中的混合物在N2下回流12小时并形成浅黄色固体。过滤该浅黄色固体并用甲醇洗涤。最后，产物从二氯甲烷-甲醇中重结晶提供浅黄色固体。收率: 35%。1H NMR (500 MHz, CD2Cl2) δ = 8.58 (dd, J = 4.8,1.3, 2H), 8.31 (dd, J = 8.5, 1.3, 2H), 8.09 – 8.04 (m, 4H), 7.82 (s, 2H),7.46 – 7.37 (m, 6H), 7.34 – 7.28 (m, 4H), 7.24 – 7.18 (m, 4H)。13C NMR (126MHz, CD2Cl2) δ = 164.25, 164.21, 162.28, 162.24, 155.40, 147.99, 141.07,138.49, 134.52, 134.49, 133.02, 132.99, 132.23, 132.16, 131.97, 131.91,131.88, 128.03, 127.42, 123.18, 116.33, 116.28, 116.23, 116.16, 116.11,51.01, 30.26, 1.34。19F NMR (376 MHz, CD2Cl2) δ = -114.16, -114.17, -114.85, -114.87。IR (KBr盘, v/cm-1): 942 (m, W=O), 903 (m, W=O)。FAB-MS (+ve, m/z): 881.0[M+]。C42H24F4N2O4W•2H2O的分析计算值: C, 50.04；H, 3.08；N, 3.06；实测值: C, 55.04；H, 3.18；N, 3.18。
实施例215 – 发射体1027的合成
配体（0.21克，0.64毫摩尔）和WO2(acac)2在干燥甲醇中的混合物在N2下回流12小时并形成浅黄色固体。过滤该浅黄色固体并用甲醇洗涤。最后，产物从二氯甲烷-甲醇中重结晶提供浅黄色固体。收率: 38%。1H NMR (600 MHz, CD2Cl2) δ = 8.61 (d, J = 5.5,2H), 8.34 (d, J = 9.5, 2H), 8.20 (d, J = 8.1, 4H), 7.88 (d, J = 8.6, 6H),7.79 (d, J = 8.2, 4H), 7.61 (d, J = 8.1, 4H), 7.46 (dd, J = 8.5, 4.8, 2H)。13CNMR (151 MHz, CD2Cl2) δ = 156.34, 148.30, 142.00, 141.02, 140.38, 138.37,131.93, 131.57, 130.06, 130.94, 130.83, 130.71, 130.62, 130.58, 130.56,130.54, 130.53, 130.47, 130.43, 130.40, 130.37, 130.35, 130.34, 130.32,130.28, 130.19, 130.07, 128.16, 127.58, 127.47, 126.99, 126.32, 126.30,126.27, 126.22, 126.20, 126.17, 126.15, 125.78, 125.66, 123.98, 123.86,123.82, 122.17, 122.06。19F NMR (376 MHz, CD2Cl2) δ = -62.81, -62.82。IR (KBr盘,v/cm-1): 956 (m, W=O), 921 (s, W=O)。FAB-MS (+ve, m/z): 1081.0 [M+]。C46H24F12N2O4W•CH3OH的分析计算值: C, 50.74；H, 2.54；N, 2.52；实测值: C, 50.56；H,2.46；N, 2.79。
实施例216 – 发射体1028的合成
配体（0.21克，0.64毫摩尔）和WO2(acac)2在干燥甲醇中的混合物在N2下回流12小时并形成浅黄色固体。过滤该浅黄色固体并用甲醇洗涤。最后，产物从二氯甲烷-甲醇中重结晶提供浅黄色固体。收率: 26%。1H NMR (400 MHz, CDCl3) δ = 7.96 (dd, J = 16.3,5.9, 15H), 7.79 (s, 3H), 7.67 (s, 3H), 7.52 (dd, J = 17.6, 9.8, 15H)。IR (KBr盘, v/cm-1): 955 (m, W=O), 917 (m, W=O)。ESI-MS (+ve, m/z): 1009.4 [M+]。C58H36N2O4W•3.5CH2Cl2的分析计算值: C, 56.56；H, 3.32；N, 2.14；实测值: C, 56.88；H,3.31；N, 2.48。
实施例217 – 发射体1013、1017、1018和1027的晶体和结构测定数据。
实施例218 - 发射体1013、1017、1018和1027的所选键长(Å)和键角(°)
透视图分别作为图301 – 304附上。
实施例219 – 光物理数据
[a] 缩写: ε = 消光系数；τ = 寿命；Φ = 发射量子产额。[b] 溶液发射量子产额(Φsol)用在脱气乙腈中的[Ru(bpy)3][PF6]2 (bpy = 2,2'-联吡啶) (Φr = 0.062)作为标准参考测量。[c] 在DCM/MeOH/EtOH混合物(v:v:v= 1:1:4)中。[d] 掺杂到MCP中的膜量子产额(Φ film )；λex = 340 nm。
实施例220 - fs-TRF测量
基于具有在350 nm波长的激发的商业Ti:蓝宝石再生式放大器激光系统（800 nm,40 fs, 1 kHz和3.5 mJ/脉冲）进行测量。通过用800 nm 基本(fundamental)激光脉冲的一部分泵浦的光学参量放大器制造350 nm泵浦激光器。通过使用Kerr门技术测量fs-TRF谱。通过800 nm激光器（探头脉冲）的一部分驱动由交叉偏振镜对和在中间的1mm厚Kerr介质（包含在石英试池中的苯）构成的Kerr装置以充当超快光学快门以在各种所选泵/探头延迟下取样瞬态荧光光谱。通过光延迟线控制探头到泵脉冲的短暂延迟。通过单色仪收集fs-TRF信号并用液氮冷却的CCD检测器检测。为了测量ns-TRE，使用同步到fs激光系统的增强型CCD（ICCD）检测器以从~2 ns向后覆盖的受控泵/探头时间延迟检测瞬态发射谱。对于所有测量，为了消除旋转扩散的效应，将泵浦激光器的偏振方向设定在相对于探头偏振方向的魔角。在室温和大气压下用在0.5 mm路径长度的试池中流动的样品溶液（~5 x10-4 M, 在CH2Cl2中）进行测量。通过UV-Vis吸收监测样品溶液并揭示在fs-TRF测量后没有降解。
实施例221 – 发射体1012、1015和1027的DFT计算
使用Gaussian 09 package进行密度泛函理论(DFT)和含时密度泛函理论(TDDFT)计算以研究钨(VI)络合物（发射体1012、1015和1027）的几何和电子结构。PBE0/6-31G*(lanl2dz)用于几何优化，且M062X/6-311G*(lanl2dz)用于三重态发射能量的TDDFT计算。使用基于PCM模型的自洽反应场（SCRF）方法考虑溶剂效应（溶剂=二氯甲烷）。结果分别描绘在图305 – 307中。
实施例222 – 发射体的电化学数据[a]
[a] 扫描速率 = 100 mVs-1。
[b] 在脱气的ACN中记录的循环伏安图。
[c] 相对于二茂铁/二茂铁盐（ferrocenium）对。Epa和Epc分别是峰值阳极和峰值阴极电位。
[d] 由氧化电位估算。EHOMO= –e (4.75 V+Epa)。
[e] 由还原电位估算。ELUMO= –e (4.75 V+Epc)。
[f] 在这一溶剂窗口中不能观察到氧化电位。
实施例223 – OLED制造程序
材料: PEDOT:PSS [聚(3,4-乙撑二氧基噻吩):聚(苯乙烯磺酸)]（Clevios P AI4083）购自Heraeus，PVK（聚乙烯基咔唑）来自Sigma-Aldrich，OXD-7 [(1,3-双[(4-叔丁基苯基)-1,3,4-噁二唑基]亚苯基)]、PYD2（2,6-二咔唑并-1,5-吡啶）、B3PYMPM [4,6-双(3,5-二(吡啶-3-基)苯基)-2-甲基嘧啶]、DPEPO（双{2-[二(苯基)膦基]-苯基}醚氧化物）和TPBi [2,2',2"-(1,3,5-benzinetriyl)-三(1-苯基-1-H-苯并咪唑)]来自LuminescenceTechnology Corp。所有材料按来样使用。
基板清洁: 带有用作OLED的基板的预图案化ITO电极的载玻片在Decon 90洗涤剂和去离子水的超声浴中清洁，用去离子水冲洗，然后在去离子水、丙酮和异丙醇的相继超声浴中清洁，随后在烘箱中干燥1小时。
器件的制造和表征: 在洁净室中将PEDOT:PSS旋涂到清洁的ITO涂布的玻璃基板上并在120℃下烘烤20分钟以除去残余水溶剂。在充满N2的手套箱内在PEDOT:PSS层上由氯苯旋涂发射层的共混物（blends of emitting layer）。所有EML的厚度为大约60 nm。此后，带有PVK和PYD2主体的器件在手套箱内分别在110和70℃下退火10分钟，随后转移到KurtJ. Lesker SPECTROS真空沉积系统中（在没有暴露于空气的情况下）。最后，在10-8毫巴的压强下通过热蒸发相继沉积B3PYMPM或DPEPO (10 nm)、TPBi (40 nm)、LiF (1.2 nm)和Al(150 nm)。通过Konica Minolta CS2000 Spectroradiometer测量EL谱、亮度和CIE坐标（coordination）。通过Keithley 2400源表测量单元测量电压-电流特征。所有器件在没有包封的情况下在室温下表征。通过假设朗伯分布，计算EQE和功率效率。
实施例224 – 由发射体1015制成的OLED的性能
发射体1015的掺杂浓度为2至6重量%。如图308中所示，发射体1015器件的EL光谱表现出宽的无特征发射，最大值位于577 nm。这样的发射符合发射体1015在mCP薄膜中的PL谱并在提高的掺杂剂浓度下保持不变，表明从PYD2主体向发射体的有效能量转移。具有2、4和6重量%掺杂剂浓度的发射体1015器件的EQE-亮度特征描绘在图309中。在具有4重量%发射体1015的器件中在~40 cd m-2的亮度下实现4.79%的最大EQE。在具有2重量%发射体1015的器件中实现最高达1400 cd m-2的高亮度。
实施例225 - 发射体1029的合成
向配体（100毫克，0.32毫摩尔）和WO2(dme)Cl2（121毫克，0.32毫摩尔）悬浮在20毫升无水二氯甲烷中的混合物中加入无水NEt3（90微升，0.65毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生黄色固体形式的产物。
收率: 82.3%。1H NMR (400 MHz, CDCl3): δ 8.18 (s, 1H), 8.05 (s, 1H),7.53–7.57 (m, 1H), 7.38–7.43 (m, 2H), 7.31 (dd, 1H, J = 1.6 Hz和7.9 Hz), 7.12(d, 1H, J = 8.2 Hz), 7.01 (t, 1H, J = 7.4 Hz), 6.73 (t, 1H, J = 7.1 Hz), 6.63(d, 1H, J = 8.6 Hz), 4.91 (d, 1H, J = 11.2 Hz), 4.35 (d, 1H, J = 12.1 Hz),3.72 (d, 1H, J = 11.1 Hz), 3.41 (d, 1H, J = 12.6 Hz), 1.65 (s, 3H), 0.78 (s,3H)；13C{1H} NMR (125 MHz, CDCl3): 168.7, 168.2, 163.9, 160.3, 138.2, 135.1,133.3, 133.2, 123.0, 122.2, 121.2, 121.0, 120.6, 118.1, 72.6, 37.7, 26.0,23.5。
实施例226 - 发射体1030的合成
向配体（100毫克，0.24毫摩尔）和WO2(dme)Cl2（92毫克，0.24毫摩尔）悬浮在20毫升无水二氯甲烷中的混合物中加入无水NEt3（71微升，0.50毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生黄色固体形式的产物。
收率: 27.3%。1H NMR (400 MHz, CDCl3): δ 8.78 (s, 1H), 8.68 (s, 1H),8.03 (d, 1H, J = 9.0 Hz), 8.00 (d, 1H, J = 8.6 Hz), 7.88 (d, 1H, J = 8.1 Hz),7.79 (d, 1H, J = 8.3 Hz), 7.73 (d, 1H, J = 9.2 Hz), 7.64 (d, 1H, J = 7.8 Hz),7.59 (t, 1H, J = 7.3 Hz), 7.53 (t, 1H, J = 7.2 Hz), 7.45 (t, 1H, J = 7.5 Hz),7.33 (t, 2H, J = 9.1 Hz), 6.56 (d, 1H, J = 9.2 Hz), 4.93 (d, 1H, J = 11.3Hz), 4.72 (d, 1H, J = 12.4 Hz), 3.89 (d, 1H, J = 11.4 Hz), 3.50 (d, 1H, J =12.5 Hz), 1.20 (s, 3H), 0.74 (s, 3H)。
实施例227 - 发射体1031的合成
向配体（111毫克，0.25毫摩尔）和WO2(dme)Cl2（94毫克，0.25毫摩尔）悬浮在20毫升无水二氯甲烷中的混合物中加入无水NEt3（69微升，0.50毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生黄色固体形式的产物。
收率: 55.1%。1H NMR (400 MHz, CDCl3): δ 7.86 (s, 1H), 7.81 (s, 1H),7.11 (dt, 2H, J = 10.1 Hz和2.2 Hz), 6.32 (d, 1H, J = 2.2 Hz), 6.27 (dd, 1H, J= 8.7 Hz和2.3 Hz), 6.18 (dd, 1H, J = 9.0 Hz和2.3 Hz), 5.96 (d, 1H, J = 2.0Hz), 4.66 (d, 1H, J = 11.6 Hz), 3.63–3.66 (m, 2H), 3.31–3.43 (m, 9H), 1.13–1.21 (m, 12H), 1.11 (s, 3H), 0.82 (s, 3H)；13C{1H} NMR (125 MHz, CDCl3): δ170.2, 164.4, 162.8, 162.2, 155.9, 153.2, 135.5, 135.0, 114.1, 112.2, 105.6,105.2, 101.3, 99.3, 78.1, 75.4, 71.2, 44.8, 44.6, 37.5, 25.8, 25.3, 12.9,12.8。
实施例228 - 发射体1032的合成
向配体（92毫克，0.18毫摩尔）和WO2(dme)Cl2（67毫克，0.18毫摩尔）悬浮在10毫升无水二氯甲烷中的混合物中加入无水NEt3（50微升，0.36毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生黄色固体形式的产物。
收率: 37.5%。1H NMR (400 MHz, CDCl3): δ 8.19 (s, 1H), 8.05 (s, 1H),7.34 (dd, 1H, J = 1.9 Hz和8.4 Hz), 7.23–7.25 (m, 1H), 7.08–7.19 (m, 9H), 6.72(d, 1H, J = 8.6 Hz), 4.95 (d, 1H, J = 11.1 Hz), 4.41 (d, 1H, J = 12.4 Hz),3.76 (d, 1H, J = 11.2 Hz), 3.45 (d, 1H, J = 12.6 Hz), 2.09 (s, 3H), 2.07 (s,6H), 2.01 (s, 3H), 1.18 (s, 3H), 0.84 (s, 3H)；13C{1H} NMR (125 MHz, CDCl3):168.7, 167.1, 163.9, 159.1, 140.1, 140.0, 139.8, 137.0, 136.4(8), 136.4(2),136.2, 136.1, 133.9, 133.4, 133.0, 130.7, 127.5, 127.4, 127.3(8), 127.3(4),127.2(8), 127.2(2), 123.1, 122.2, 121.3, 120.8, 76.9, 73.1, 37.8, 26.0, 23.7,21.0, 20.9, 20.8。
实施例229 - 发射体1033的合成
向配体（100毫克，0.17毫摩尔）和WO2(dme)Cl2（65毫克，0.17毫摩尔）悬浮在10毫升无水二氯甲烷中的混合物中加入无水NEt3（48微升，0.34毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生黄色固体形式的产物。
收率: 32.2%。1H NMR (400 MHz, CDCl3): δ 8.19 (s, 1H), 8.06 (s, 1H),7.52 (dd, 1H, J = 2.0 Hz和8.5 Hz), 7.46 (dd, 1H, J = 2.5 Hz和8.8 Hz), 7.37(d, 1H, J = 2.5 Hz), 7.33 (d, 1H, J = 2.5 Hz), 7.24–7.30 (m, 2H), 7.12 (d,1H, J = 8.5 Hz), 6.78 (d, 1H, J = 8.5 Hz), 6.66 (d, 2H, J = 8.5 Hz), 6.62 (d,2H, J = 8.5 Hz), 4.92 (d, 1H, J = 11.0 Hz), 4.14 (d, 1H, J = 12.5 Hz), 3.71–3.74 (m, 13H), 3.46 (d, 1H, J = 12.5 Hz), 1.17 (s, 3H), 0.83 (s, 3H)；13C{1H}NMR (100 MHz, CDCl3): δ 168.8, 167.4, 164.3, 159.2, 157.9, 157.8, 142.0,138.3, 136.0, 135.6, 129.0, 128.7, 127.1, 123.7, 122.6, 121.9, 120.5, 119.8,118.1, 117.9, 104.4, 104.3, 76.6, 72.8, 56.1, 55.9, 37.6, 26.2, 24.6。
实施例230 - 发射体1034的合成
向配体（80毫克，0.17毫摩尔）和WO2(dme)Cl2（64毫克，0.17毫摩尔）悬浮在20毫升无水二氯甲烷中的混合物中加入无水NEt3（47微升，0.34毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生橙色固体形式的产物。
收率: 55.1%。1H NMR (400 MHz, CDCl3): δ 8.25 (s, 1H), 8.11 (s, 1H),7.81 (dd, 1H, J = 8.6 Hz和2.2 Hz), 7.66 (dd, 1H, J = 8.8 Hz和2.2 Hz), 7.62(d, 1H, J = 2.0 Hz), 7.52 (d, 1H, J = 2.2 Hz), 7.26–7.28 (m, 2H), 7.20 (d,1H, J = 5.0 Hz), 7.15 (d, 1H, J = 8.6 Hz), 7.12 (d, 1H, J = 3.4 Hz), 7.09 (t,1H, J = 4.4 Hz), 7.03 (t, 1H, J = 4.5 Hz), 6.67 (d, 1H, J = 8.9 Hz), 4.92 (d,1H, J = 11.1 Hz), 4.44 (d, 1H, J = 12.4 Hz), 3.77 (d, 1H, J = 11.2 Hz), 3.43(d, 1H, J = 12.6 Hz), 1.18 (s, 3H), 0.79 (s, 3H)。
实施例231 - 发射体1035的合成
向配体（80毫克，0.12毫摩尔）和WO2(dme)Cl2（50毫克，0.13毫摩尔）悬浮在10毫升无水四氢呋喃中的混合物中加入无水NEt3（35微升，0.25毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生淡红橙色固体形式的产物。
收率: 25.2%。1H NMR (500 MHz, CDCl3): δ 8.02 (s, 1H), 7.90 (s, 1H),7.34 (t, 1H, J = 3.0 Hz), 7.33 (t, 1H J = 2.5 Hz), 7.20–7.27 (m, 8H), 7.12(d, 1H, J = 3.0 Hz), 7.07 (s, 2H), 7.02–7.05 (m, 8H), 7.00 (s, 1H), 6.97 (t,3H, J = 7.5 Hz), 6.69 (d, 1H, J = 9.0 Hz), 4.87 (d, 1H, J = 11.5 Hz), 4.21(d, 1H, J = 12.5 Hz), 3.65 (d, 1H, J = 11.0 Hz), 3.37 (d, 1H, J = 12.5 Hz),1.12 (s, 3H), 0.77 (s, 3H)；13C{1H} NMR (150 MHz, CDCl3): δ 168.0, 165.4,163.6, 156.5, 147.6, 147.6, 141.2, 138.4, 137.4, 132.3, 129.3, 129.3, 128.7,128.2, 123.5, 123.4, 123.2, 122.6, 122.3, 122.3, 121.6, 76.6, 72.8, 37.63,26.0, 24.0。
实施例232 - 发射体1036的合成
向配体（70毫克，0.22毫摩尔）和WO2(dme)Cl2（43毫克，0.11毫摩尔）悬浮在10毫升无水二氯甲烷中的混合物中加入无水NEt3（40微升，0.29毫摩尔）。将反应混合物在N2气氛下加热至回流整夜。该粗产物经硅藻土过滤以除去不溶物。收集滤液并用水和二氯甲烷萃取。在减压下除去溶剂。随后用己烷或二氯甲烷/乙酸乙酯(4:1)的柱色谱法产生黄色固体形式的产物。
收率: 35.4 %。1H NMR (500 MHz, CDCl3): δ 8.71 (dd, 1H, J = 4.8 Hz和1.3Hz), 8.28 (dd, 1H, J = 8.8 Hz和1 Hz), 7.47 (d, 1H, J = 8 Hz), 7.37 (d, 1H, J= 8 Hz), 7.34 (dd, 1H, J = 8.8 Hz和4.8 Hz)；7.20 (t, 4H, J = 7.5 Hz), 6.95–6.97 (m, 6H)；13C{1H} NMR (150 MHz, CDCl3): δ 157.0, 148.1, 147.3, 140.8,136.8, 135.8, 130.1, 129.4, 127.5, 122.6, 122.4, 122.1, 116.1。
实施例233 – 发射体1031和1034的晶体和结构测定数据
实施例234 - 发射体1031和1034的所选键长(Å)和键角(°)
实施例235 - 发射体1031和1034的所选键长(Å)和键角(°)
实施例236 – 光物理数据
实施例237 – 发射体的电化学数据[a]
[a] 扫描速率 = 100 mVs-1。
[b] 在脱气CH2Cl2中记录循环伏安图。
[c] 相对于二茂铁/二茂铁盐对。Epa和Epc分别是峰值阳极和峰值阴极电位。
[d] 由氧化电位估算。EHOMO= –e (4.75 V+Epa)。
[e] 由还原电位估算。ELUMO= –e (4.75 V+Epc)。
[f] 准可逆波的E1/2 [E1/2 = (Epc + Epa)/2]。
关于给定特征的任何数值或数值范围，来自一个范围的数值或参数可与来自同一特征的不同范围的另一数值或参数组合以生成数值范围。
除了在操作实施例中或在另行指明之处外，说明书和权利要求书中所用的关于成分量、反应条件等的所有数值、值和/或表达式（expressions）应被理解为在所有情况下都被术语“大约”修饰。
应该理解的是，本文中描述的实施例和实施方案仅用于举例说明的目的，且基于其的各种修改或变动是本领域技术人员会想到的，并包括在本申请的精神和范围内。
Claims (5)
1.一种OLED发射体，其选自发射体1001-发射体1028：
2.一种OLED发射体，其选自发射体1029–1036：
3.一种发光器件，其包含至少一种如权利要求1-2任一项中的OLED发射体作为发射材料。
4.一种发光器件，其包含以下发射体作为发射材料：
5.权利要求3的发光器件，其中所述器件是有机发光二极管；和/或
其中所述器件通过真空沉积制造；和/或
其中所述器件通过溶液法制造；和/或
其中掺杂剂浓度大于5重量％；和/或
其中所述器件含有一个发射层；和/或
其中所述器件含有多于一个发射层。
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