CN107200755A - platinum complex coordinated by four-coordinate deuterated ligand - Google Patents

Abstract

Translated fromChinese

本发明的是关于一种适合在显示和照明应用中用作磷光或延迟荧光或磷光发射体的多齿配位的铂络合物，所述适合用作磷光发射体或用作延迟荧光或磷光发射体的铂络合物具有以下结构之一：

The present invention relates to a multidentate coordinated platinum complex suitable for use as a phosphorescent or delayed fluorescent or phosphorescent emitter in display and lighting applications, which is suitable for use as a phosphorescent emitter or as a delayed fluorescent or phosphorescent The platinum complex of the emitter has one of the following structures:

Description

Translated fromChinese

四配位氘代配体配位的铂络合物Platinum complexes coordinated by tetracoordinated deuterated ligands

技术领域technical field

本发明的公开内容是关于一种适合在显示和照明应用中用作磷光或延迟荧光或磷光发射体的的多齿配位的铂络合物。The present disclosure relates to a multidentate coordinated platinum complex suitable for use as phosphorescent or delayed fluorescent or phosphorescent emitters in display and lighting applications.

背景技术Background technique

能够吸收和/或发光的化合物可适用于各种光学和光电器件，包括但不限于诸如太阳能、光敏这样的光吸收器件、有机发光二极管(OLED)、光发射器件或既有光吸收又有光发射能力的器件以及用于生物标记的相关应用。为了发现用于光学和电致发光器件的有机和有机金属材料，已专门作过很多研究。一般而言，这一领域的研究目村是实现多项目标，包括提高器件的吸收和发光效率，提高器件的稳定性，以及提高分辨率等。Compounds capable of absorbing and/or emitting light are applicable to a variety of optical and optoelectronic devices, including but not limited to light-absorbing devices such as solar, photosensitive, organic light-emitting diodes (OLEDs), light-emitting devices, or both light-absorbing and light-emitting devices. Emissive capable devices and related applications for biomarkers. Much research has been dedicated to the discovery of organic and organometallic materials for use in optical and electroluminescent devices. Generally speaking, research in this field aims to achieve multiple goals, including improving the absorption and luminescence efficiency of the device, improving the stability of the device, and improving the resolution.

尽管专门为光学和光电材料(例如，红色和绿色磷光有机金属材料在市面上有售并且已在有机发光二极管(OLED)、照明和先进显示器中用作磷光体)所作的研究取得了显著的进步，但许多目前可获得的材料表现出不少缺点，包括综合性能一般、发射或吸收不足以及稳定性不够理想等等。Despite significant progress in research specifically for optical and optoelectronic materials (for example, red and green phosphorescent organometallic materials are commercially available and have been used as phosphors in organic light-emitting diodes (OLEDs), lighting and advanced displays) , but many currently available materials show many shortcomings, including general performance, insufficient emission or absorption, and unsatisfactory stability.

优良的蓝色发射体尤其稀少，其面对的一大挑战是蓝色器件的稳定性。与红色及绿色磷光体的最低三重激发态能量相比，蓝色磷光体的最低三重激发态能量很高，这意味着蓝色器件的主体材料的最低三重激发态能量甚至会更高。因此，问题之一是蓝色器件可用的掺杂材料是有限的。相应地，需要能够在光学发射和吸收应用中表现出更优性能的新材料。Excellent blue emitters are especially rare, and a major challenge is the stability of blue devices. Compared with the lowest triplet excited state energy of red and green phosphors, the lowest triplet excited state energy of the blue phosphor is very high, which means that the lowest triplet excited state energy of the host material of the blue device is even higher. Therefore, one of the problems is that the available dopant materials for blue devices are limited. Accordingly, new materials capable of exhibiting improved performance in optical emission and absorption applications are required.

在本发明的公开内容中，将氘引入铂络合物的配体。由于氘原子比氢原子重，与C-H键相比，碳-氘(C-D)键的振动可以减少。因此，发射光谱的振动带将减少或削弱，而整个光谱可以变窄。这将能够促进发射光色并改善器件的性能。更明确地说，络合物的CIE坐标将被调谐成更符合平板电视的需求。In the present disclosure, deuterium is introduced into the ligands of the platinum complex. Since a deuterium atom is heavier than a hydrogen atom, the vibration of a carbon-deuterium (C-D) bond can be reduced compared to a C-H bond. Consequently, the vibrational bands of the emission spectrum will be reduced or weakened, and the entire spectrum can be narrowed. This would be able to boost the color of the emitted light and improve the performance of the device. More specifically, the CIE coordinates of the complex will be tuned to more closely match the needs of flat-panel televisions.

发明内容Contents of the invention

本发明涉及适合在有机发光二极管(OLED)、显示和照明应用中的用作发射体的金属络合物。The present invention relates to metal complexes suitable for use as emitters in organic light emitting diodes (OLEDs), display and lighting applications.

此处公开的是1型分子式络合物：Disclosed here is a type 1 complex of formula:

R^a代表单、双、三或四基取代，R^a是独立的氘，CDH₂，CD₂H，CD₃，CD R¹R²，CD₂R¹，或其他含氘的烷基芳、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单取代氨基、二烃基氨基、单氨基、二芳基胺、烷氧基、芳氧基、卤代基、芳烷基、酯、烷氧羰基、酰胺基、烷氧基羰基氨基，烷氧基碳酰基氨基、芳氧基碳酰基氨基、芳烷基、氨磺酰、氨基甲酰基、烷硫基，脲基、磷酰胺、甲硅烷基、聚合物；或其任何结合物或化合物。R^a represents mono-, di-, tri- or tetra-substitution, R^a is independent deuterium, CDH₂ , CD₂ H, CD₃ , CD R¹ R² , CD₂ R¹ , or other deuterium-containing alkyl aromatics, Cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monosubstituted amino, dihydrocarbylamino, monoamino, diarylamine, alkoxy, aryloxy , halo, aralkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aralkyl, sulfamoyl, carbamoyl, Alkylthio, ureido, phosphoramide, silyl, polymer; or any combination or compound thereof.

R^b、R^c、R^d和R^e中的每一种都是要么独立存在的或不存在的；如果是存在的，那么R^b、R^c、R^d和R^e中的每一种分别代表单或双基取代，R^b,R^d和R^e也可以是三基取代，R^b可以是四基取代，并且其中R^b、R^c、R^d和R^e中的每一种是独立的氘、卤素、羟基、巯基、硝基、氰基、腈、异腈、亚磺酰基、巯基、磺基、羧基、肼基；取代或未取代的：芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤代烷基、芳烷基、酯、烷氧基羰基、酰基氨基、烷氧基羰基氨基、芳基含氧羰基氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物，R^a和R^b可选择性地连接形成环，R^d和R^e可选择性地连接形成环。Each of R^b , R^c , R^d and^Re is either independently present or absent; if present, each of R^b , R^c , R^d and^Re respectively Represents single or double substitution, R^b , R^d and^Re may also be tri-substitution, R^b may be tetra-substitution, and each of R^b , R^c , R^d and^Re is independently Deuterium, halogen, hydroxyl, mercapto, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl , heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl , aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, sulfonamide, carbamoyl, alkylthio, ureido, phosphoramide, Silyl, polymerization; or any combination or compound thereof, R^a and R^b may be optionally connected to form a ring, and R^d and R^e may be optionally connected to form a ring.

R¹和R²中的每一种都是独立的氢、氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、氧芳基、卤烷基、芳烷基,、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、硫烷基、脲基、磷酰胺、甲硅烷基、聚合物；或其任何结合物或化合物。Each^of R and R is independently^hydrogen , deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternative or irreplaceable: aryl, cycloalkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkyl Amino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, Aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, sulfanyl, ureido, phosphoramide, silyl, polymer; or any combination or compound thereof.

一方面，该铂络合物具有分子式2、分子式3、分子式4、分子式5、分子式6或分子式7的结构。另一方面，它们也可以包含其在这没有得到专门详述的其他结构或部分，本发明不应局限于其那些在此得到专门详述的结构或部分。In one aspect, the platinum complex has the structure of formula 2, formula 3, formula 4, formula 5, formula 6 or formula 7. On the other hand, they may also contain other structures or parts thereof that are not specifically described in detail here, and the present invention should not be limited to those structures or parts thereof that are specifically described in detail here.

R^b、R^c、R^d和R^e中的每一种都是要么独立存在的或不存在的，如果是存在的，那么R^b、R^c、R^d和R^e中的每一种分别代表单或双基取代，R^b,R^d和R^e也可以是三基取代，R^b可以是四基取代，并且其中R^b、R^c、R^d和R^e中的每一种是独立的氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；替代或不替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物，R^a和R^b可选择性地连接形成熔合环，R^d和R^e可选择性地连接形成熔合环。Each of R^b , R^c , R^d and^Re is either independently present or absent, and if present, each of R^b , R^c , R^d and^Re respectively Represents single or double substitution, R^b , R^d and^Re may also be tri-substitution, R^b may be tetra-substitution, and each of R^b , R^c , R^d and^Re is independently deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternatively or not: aryl, cyclic Alkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino , alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, sulfonamide, carbamoyl, alkane Thio group, ureido group, phosphoramidite, silyl group, polymerization; or any combination or compound thereof, R^a and R^b can be optionally linked to form a fusion ring, R^d and R^e can be optionally linked to form a fusion ring .

R¹和R²中的每一种都是独立的氢、氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物。Each^of R and R is independently^hydrogen , deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternative or irreplaceable: aryl, cycloalkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkyl Amino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxy Carbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any combination or compound thereof.

本文还公开了包括在本文中公开的一种或多种化合物的组合物。Also disclosed herein are compositions comprising one or more compounds disclosed herein.

本文还公开了包括在本文中公开的一种或多种化合物的器件，比如有机发光二极管。Also disclosed herein are devices, such as organic light emitting diodes, comprising one or more compounds disclosed herein.

附图说明Description of drawings

图1描述了一个包含本文所公开金属络合物的器件。在一具体实施例中，该化合物可在有机发光二极管中使用。Figure 1 depicts a device comprising a metal complex disclosed herein. In a specific embodiment, the compound can be used in organic light emitting diodes.

图2显示了室温下复合物1在CH₂Cl₂和PMMA中的发射光谱。Figure₂ shows the emission spectra of complex 1 in_CH2Cl2 and PMMA at room temperature.

图3显示了在⁶d-DMSO溶剂中含氘复合物3和不含氘复合物的¹H NMR图谱比较。Figure 3 shows the comparison of the¹ H NMR spectra of the deuterium-containing complex 3 and the deuterium-free complex in⁶ d-DMSO solvent.

图4显示了室温下复合物3在CH₂Cl₂和PMMA中的发射光谱。Figure 4 shows the emission spectra of complex₃ in_CH2Cl2 and PMMA at room temperature.

图5显示了室温下复合物3在CH₂Cl₂中的含氘复合物和不含氘复合物发射光谱的比较。Figure 5 shows a comparison of the emission spectra of complex₃ in_CH2Cl2 at room temperature with and without deuterium.

图6显示了室温下复合物2在PMMA中的含氘复合物和不含氘复合物发射光谱的比较。Figure 6 shows a comparison of the emission spectra of complex 2 in PMMA with and without deuterium at room temperature.

图7显示了室温下复合物7在CH₂Cl₂中的含氘复合物和不含氘复合物发射光谱的比较。Figure 7 shows a comparison of the emission spectra of complex₇ in_CH2Cl2 at room temperature with and without deuterium.

在图片后的图片描述中对图片的其它方面也进行了描述。优势是通过在权利要求中特别指出的元素和组合而实现及获得的。需要指出的是，上面的一般说明和下面的详细说明都只是示范性和解释性的，不具有限定性。Other aspects of the image are also described in the image description following the image. The advantages are realized and attained by means of the elements and combinations particularly pointed out in the claims. It should be pointed out that the above general description and the following detailed description are only exemplary and explanatory, not limiting.

具体实施方式detailed description

通过参考以下详细说明和其中包含的示例，可以更容易地理解本发明。The present invention can be understood more readily by reference to the following detailed description and the Examples contained therein.

在本发明化合物、器件和/或方法被公开和描述之前，应当指出的是，除非另有说明，否则它们不限于特定的合成方法，或者除非另有说明，否则它们不限于特定试剂，因为这些方法或试剂当然可以更改。还要指出的一点是，本文中所用的术语只是为了描述特定的方面，而不是为了限制。尽管与本文中所描述的那些方法或材料类似或相同的任何方法或材料都可以在实践或测试中使用，但现在描述的是示例性方法和材料。Before the compounds, devices and/or methods of the present invention are disclosed and described, it should be noted that they are not limited to specific synthetic methods unless otherwise indicated, or to specific reagents unless otherwise indicated, because these Methods or reagents may of course be altered. It is also to be noted that the terminology used herein is for the purpose of describing particular aspects only and not for limitation. Although any methods or materials similar or equivalent to those described herein can be used in the practice or testing, exemplary methods and materials are now described.

除非上下文另有其它明确规定，否则说明和附加权利要求中使用的单数形式“一”、“一”和“某一”包括复数指称。因此，例如，提到“一种成分”时包括两种或两种以上成分的混合。As used in the description and appended claims, the singular forms "a," "an," and "an" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an ingredient" includes a mixture of two or more ingredients.

本文中使用的术语“可选的”或“可选地”指的是随后描述的事件或情况可能会发生或可能不会发生，并且该描述包括所述事件或情况发生时的具体实施例和该事件或情况不发生时的具体实施例。As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes specific examples and A specific example of when the event or circumstance does not occur.

本文公开的是用于制备本文所述组合物以及在本文公开的方法中要使用的组合物本身的成分。这些和其他材料在本文中得到公开，要指出的是，当这些材料的组合、亚群、相互作用、类被公开时，虽然这些复合物的每一不同的单独和集体组合和排列的特定引用不能得到明确公开，但每一复合物都在本文中得到特别考虑和描述。例如，如果一特定化合物得到公开和讨论并且对于包含所述化合物的多个分子所能做的多种修改得到讨论，除非进行了相反地特别说明，否则该化合物的每一组合和排列以及可能的修改都会得到考虑。因此，如果属于同一类的分子A、B和C以及属于同一类的分子D，E和F以及一种组合分子的示例得到公开，那么A-D得到了公开，那么这样的话，即使不是每一分子都得到单独详述，每一分子都得到单独和集体考虑的意思仍然是，A-E，A-F，B-D，B-E，B-F，C-D，C-E和C-F的组合都被认为得到了公开。同样，这些分子的子集或组合也被认为得到了公开。因此，比如，A-E，B-F和C-E的子群会被认为得到了公开。这个概念适用于该应用的所有方面，包括，但不限于，制备和使用该组合物的方法中的步骤。因此，如果存在能够执行的各种各样的额外步骤，对此可以理解为，可以用这些方法的任一特定具体实施例或具体实施例组合执行这些额外步骤中的每一种。Disclosed herein are the ingredients used to prepare the compositions described herein, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is noted that when combinations, subgroups, interactions, species of these materials are disclosed, although specific reference to each of the various individual and collective combinations and permutations of these compounds Not explicitly disclosed, but each complex is specifically considered and described herein. For example, if a particular compound is disclosed and discussed and the various modifications that can be made to molecules comprising said compound are discussed, unless specifically stated to the contrary, every combination and permutation of that compound and possible Amendments will be considered. Thus, if examples of molecules A, B, and C belonging to the same class and molecules D, E, and F belonging to the same class and a combination of molecules are disclosed, A-D are disclosed, so that even if not every molecule To be recited individually, each molecule considered individually and collectively still means that the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F are all considered disclosed. Likewise, subsets or combinations of these molecules are considered disclosed. Thus, for example, subgroups A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions. Thus, where there are various additional steps that can be performed, it is understood that each of these additional steps can be performed with any particular embodiment or combination of embodiments of these methods.

如本文所提到的那样，一个连接原子或基团可以连接两个原子，比如，一个氮原子和一个碳原子。一个连接原子或集团在本文中一方面被公开为X，Y，Y¹，Y²，和/或Z。如果化合价允许的话，该连接原子还可以选择性拥有附着的其他化学基团。例如，一方面，因为如果化合价一旦被结合到两基团上(例如，氮和碳基团)，它就会饱和，所以一个氧原子不会有任何附着的其他化学基团。另一方面，当碳原子是连接原子时，可以为碳原子附着两个额外的化学基团。合适的化学基团包括胺、酰胺、硫醇、芳基、杂芳基、环烷基烷基和杂环基基团。As referred to herein, a linking atom or group can link two atoms, eg, a nitrogen atom and a carbon atom. A linking atom or group is disclosed herein as X, Y,^Y1 ,^Y2 , and/or Z in one aspect. The linking atom may also optionally have other chemical groups attached, if valence permits. For example, on the one hand, an oxygen atom would not have any other chemical groups attached because it would be saturated if the valence were once bonded to two groups (eg, nitrogen and carbon groups). On the other hand, when the carbon atom is the linking atom, two additional chemical groups can be attached to the carbon atom. Suitable chemical groups include amine, amide, thiol, aryl, heteroaryl, cycloalkylalkyl and heterocyclyl groups.

术语“循环结构”或类似术语在本文中指的是任何循环化学结构，包括但不限于，芳基、杂芳基、环烷基烷基、环烯基、杂环基、碳烯和N-杂环基碳烯。The term "cyclic structure" or similar terms herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkylalkyl, cycloalkenyl, heterocyclyl, carbene, and N-hetero Cyclocarbene.

在本文中使用的“替代”一词被设想为包括有机化合物的所有可允许取代基。在一个广泛的方面上，可允许取代基包括有机化合物的非环状和环状的，支链和无支链的，碳环和杂环的，芳香族和非芳香族的取代基。说明性的取代基包括，例如，下文所描述的那些取代基。对合适的有机化合物来说，可允许取代基可以是一个或多个，可以相同或不同。为了实现本发明的目的，杂原子，如硝基，可以拥有本文所描述的满足杂原子化合价的有机化合物的氢取代基和/或任何可允许的取代基。本发明不会以任何方式受到有机化合物的可允许取代基的限制。另外，术语“取代”或“以...取代”包括的隐含条件是，这样的取代与取代原子和取代基的可允许化合价相一致，并且这种取代会带来一种稳定的化合物，比如，一种不会自发通过重排、环化、消除等方式进行转换的化合物。我们还做出的设想是，在某些方面，除非有明确相反的说明，单个取代基可以被进一步选择性取代(即，进一步取代的或未取代的)。The word "substituent" as used herein is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents may be one or more, and may be the same or different, for appropriate organic compounds. For the purposes of the present invention, a heteroatom, such as a nitro group, may possess hydrogen substituents and/or any permissible substituents of organic compounds described herein that satisfy the valences of the heteroatom. This invention is not limited in any way by the permissible substituents of organic compounds. In addition, the term "substituted" or "substituted with" includes the implicit proviso that such substitution is consistent with the permissible valences of the substituting atom and substituent, and that such substitution will result in a stable compound, For example, a compound that does not undergo spontaneous transformation by rearrangement, cyclization, elimination, etc. It is also contemplated that in some aspects, unless expressly stated to the contrary, individual substituents may be further selectively substituted (ie, further substituted or unsubstituted).

为了定义不同的属于，“A1”、“A2”、“A3”、“A4”在本文中用于作为代表各种特定取代基的通用符号。这些符号可以是任何取代基，不限于那些在本文中得到公开的取代基，如果他们在一具体实施例中被定义为特定取代基，他们能，在另一具体实施例中，被定义为一些其它取代基。"A1", "A2", "A3", "A4" are used herein as general symbols to represent various specific substituents in order to define different genus. These symbols can be any substituents, not limited to those substituents disclosed herein, if they are defined as specific substituents in one embodiment, they can, in another embodiment, be defined as some other substituents.

本文中使用的术语“烷基”是一种支链或无支链的由1到24个碳原子组成的饱和碳氢化合物集团，比如甲基、乙基、正丙基、异丙基、正丁基、异丁基、二丁基、叔丁基、正戊基、异戊基、二戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二基、十四基、十六基、二十基、二十四基等。烷基团可以是环状的或非环状的。烷基团可以是支链或无支链的。烷基团也可以是可取代的或不可取代的。比如，烷基团可以用一个或多个集团取代，包括但不限于，本文所描述的烷基、环烷基烷基、烷氧基、氨基，或者，卤化物、羟基、硝基、甲硅烷基、磺氧基或硫醇。一种“低烷基”基团是一种包含从1到6(比如从1到4)个不等的碳原子的烷基团。The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group consisting of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, dibutyl, tert-butyl, n-pentyl, isopentyl, dipentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, deca Four bases, sixteen bases, twenty bases, twenty four bases, etc. Alkyl groups can be cyclic or acyclic. Alkyl groups may be branched or unbranched. Alkyl groups may also be substituted or unsubstituted. For example, an alkyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkylalkyl, alkoxy, amino as described herein, or, halide, hydroxy, nitro, silyl group, sulfoxy group or thiol. A "lower alkyl" group is an alkyl group containing from 1 to 6, such as from 1 to 4, carbon atoms.

在本文的通篇描述中，“烷基”一般是指未取代烷基组和取代烷基组两者；然而，在本文中，也通过特别确认烷基组上的特别取代基，提到取代烷基组。例如，术语“卤烷”或“卤代烷基”具体指一种被一个或多个卤化物，如氟、氯、溴或碘取代的烷基组。术语“烷氧基烷基”具体指被一个或多个如下文所述烷氧基团所取代的一种烷基团。术语“烷基氨基”具体指被一个或多个如下文所述烷氨基团等所取代的一种烷基团。当在一个具体实施例中使用“烷基”，而在另一个具体实施例中使用诸如“烷基乙醇”之类特定术语时，不意味着这是在暗示，“烷基”这个术语不是指的也是诸如“烷基乙醇”等之类特定术语。Throughout the description herein, "alkyl" generally refers to both unsubstituted and substituted alkyl groups; however, references to substituted Alkyl group. For example, the term "haloalkane" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halides, such as fluorine, chlorine, bromine or iodine. The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more alkylamino groups, etc. as described below. When "alkyl" is used in one embodiment and a specific term such as "alkylethanol" in another embodiment, it is not meant to imply that the term "alkyl" does not refer to There are also specific terms such as "alkyl alcohols" and so on.

这种做法也适用于本文所述的其他基组。也就是，一个诸如“环烷基”之类术语指的是非取代性和取代性环烷基烷基基团两者，另外，取代性基团也可以在文章中得到具体确定；例如，一种特别的取代性环烷基可以北称为，比如，一种“环烷基”。同样，一种取代性烷氧基可以被专门称为，例如，“卤化烷氧基”，一种特别取代性烯基可以被称为，例如，“烯基乙醇”，或类似的术语。再次，使用诸如“环烷基”之类一般术语和诸如“烷基环烷基”之类特定术语并不意味着，一般术语不是也包括特定术语。This practice also applies to the other basis groups described in this paper. That is, a term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkylalkyl groups, additionally, substituent groups may also be specifically identified in the text; for example, a A particular substituted cycloalkyl group can be referred to, for example, as a "cycloalkyl group." Likewise, a substituted alkoxy group may be referred to specifically, for example, "halogenated alkoxy", and a particular substituted alkenyl group may be referred to, for example, "alkenyl alcohol", or similar terms. Again, use of a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" does not imply that the general term does not also include the specific term.

本文中使用的术语“环烷基”是一种至少由三个碳原子所组成的非芳香碳基环。环烷基烷基组的例子包括，但不限于，环丙烷，环丁烷，环戊烷，环己基，降冰片基，以及类似的物质。术语“杂环烷基”是一种如上文所定义的环烷基团，并包括在“环烷基“”的含义之中，在这个含义中，环上的至少一个碳原子被一个杂原子所取代，这种杂原子包括，但不限于，氮、氧、硫或磷。环烷基组和杂环烷基组可以是取代性的或非取代性的。环烷基组和杂环烷基组可以被一个或多个基组取代，包括，但不限于，本文所描述的烷基、环烷基、烷氧基、氨基、醚、卤、羟基、硝基、甲硅烷基、磺氧基，或硫醇。The term "cycloalkyl" as used herein is a non-aromatic carbonyl ring consisting of at least three carbon atoms. Examples of cycloalkylalkyl groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexyl, norbornyl, and the like. The term "heterocycloalkyl" is a cycloalkyl group as defined above and is included within the meaning of "cycloalkyl" in which at least one carbon atom of the ring is replaced by a heteroatom Substituted, such heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur or phosphorus. Cycloalkyl groups and heterocycloalkyl groups may be substituted or unsubstituted. Cycloalkyl groups and heterocycloalkane The radical group may be substituted with one or more radical groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halo, hydroxyl, nitro, silyl, sulfoxy as described herein base, or thiol.

本文中使用的术语“聚亚烃基组”是一种有两个或多个彼此相连的CH2基团的基组。聚亚烃基组可由分子式—(CH₂)_a—表示，其中一“a”代表一个从2到500的整数。The term "polyalkylene group" as used herein is a group having two or more CH2 groups attached to each other. The polyalkylene group can be represented by the molecular formula -(CH₂ )_a -, wherein an "a" represents an integer from 2 to 500.

本文中使用的术语“烷氧基的”和“烷氧基”指的是一种通过一个醚键相连的烷基或环烷基组；也就是，一种“烷氧基”组可以被定义为—OA¹，其中A¹是上文定义的烷基或环烷基。“烷氧基”也包括刚刚描述的烷氧基组的聚合物；也就是，一种烷氧基可以是一种诸如—OA¹—OA²或—OA¹—(OA²)_a—OA³之类的聚合物，其中“a”是一个从1到200的整数，而A¹、A²和A³是烷基和/或环烷基组。As used herein, the terms "alkoxy" and "alkoxy" refer to an alkyl or cycloalkyl group linked through an ether linkage; that is, an "alkoxy" group can be defined is —OA¹ , wherein A¹ is an alkyl or cycloalkyl group as defined above. "Alkoxy" also includes polymers of the alkoxy group just described; that is, an alkoxy group may be one such as -OA¹ -OA² or -OA¹ -(OA² )_a -OA³ Polymers such as , wherein "a" is an integer from 1 to 200, and A¹ , A² and A³ are alkyl and/or cycloalkyl groups.

本文所使用的术语“烯基”是一种包含2到24个碳原子的碳氢化合物集团，它的结构分子式至少含有一个碳碳双键。诸如(A¹A²)C＝C(A³A⁴)之类的非对称结构旨在包括E和Z两种异构体。这可以从结构分子式中推定，在结构分子式中，存在一种不对称的烯烃，或者也可以用C＝C键符号明确表示它。烯基团可以用一个或多个基团取代，包括但不限于，本文所描述的烷基,环烷基烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、异芳基、乙醛、氨基、羧酸、酯、醚、卤化物、羟基、酮、叠氮化物、硝基、甲硅烷基、磺氧基或硫醇。The term "alkenyl" as used herein refers to a hydrocarbon group containing 2 to 24 carbon atoms, whose structural formula contains at least one carbon-carbon double bond. Asymmetric structures such as (A¹ A² )C=C(A³ A⁴ ) are intended to include both E and Z isomers. This can be deduced from the structural formula, in which an asymmetric alkene is present, or it can be explicitly indicated by the C=C bond symbol. Alkenyl groups may be substituted with one or more groups, including, but not limited to, alkyl, cycloalkylalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, as described herein. radical, heteroaryl, acetaldehyde, amino, carboxylic acid, ester, ether, halide, hydroxyl, ketone, azide, nitro, silyl, sulfoxy, or thiol.

本文中使用的术语“环烯基”是一种由至少三个碳原子组成的非芳香碳环，并且至少含有一个碳碳双键，即C＝C。环烯基组的例子包括，但不限于，环丙烯基、环丁烯基、环戊烯基、环十五烯基、环己烯、环己二烯基、降冰片烯，以及类似化合物。术语“杂环烯基”是一类上文所定义的环烯基组，并且包括在术语“环烯基”的含义中，其中环上的至少一个碳原子被一杂原子所取代，该杂原子包括但不限于，氮、氧、硫、磷。环烯基组和杂环烯基组可以是取代性的和非取代性的。环烯基组和杂环烯基组可以被一种或多种组取代，包括但不限于，本文所描述的烷基、环烷基、烷氧基,、烯基、环烯基、炔基、环炔基、芳基、杂芳基、乙醛、氨基、羧酸、酯、醚、卤、羟基、酮、叠氮、硝基、甲硅烷基、磺氧基或硫醇。The term "cycloalkenyl" as used herein is a non-aromatic carbocyclic ring consisting of at least three carbon atoms and containing at least one carbon-carbon double bond, ie C=C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadecenyl, cyclohexene, cyclohexadienyl, norbornene, and the like. The term "heterocycloalkenyl" is a class of cycloalkenyl groups as defined above and is included within the meaning of the term "cycloalkenyl" in which at least one carbon atom of the ring is replaced by a heteroatom which Atoms include, but are not limited to, nitrogen, oxygen, sulfur, phosphorus. Cycloalkenyl groups and heterocycloalkenyl groups may be substituted and unsubstituted. Cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl as described herein , cycloalkynyl, aryl, heteroaryl, acetaldehyde, amino, carboxylic acid, ester, ether, halo, hydroxyl, ketone, azide, nitro, silyl, sulfoxy, or thiol.

本文所使用的术语“炔基”是一种包含2到24个碳原子的碳氢化合物集团，它的结构分子式至少含有一个碳碳三键。炔基团可以用一个或多个基团取代，包括但不限于，本文所描述的烷基、环烷基烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、异芳基、乙醛、氨基、羧酸、酯、醚、卤化物、羟基、酮、叠氮化物、硝基、甲硅烷基、磺氧基或硫醇。As used herein, the term "alkynyl" is a hydrocarbon group containing 2 to 24 carbon atoms whose structural formula contains at least one carbon-carbon triple bond. Alkyne groups may be substituted with one or more groups, including, but not limited to, alkyl, cycloalkylalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl radical, heteroaryl, acetaldehyde, amino, carboxylic acid, ester, ether, halide, hydroxyl, ketone, azide, nitro, silyl, sulfoxy, or thiol.

本文中使用的术语“环炔基”是一种由至少七个碳原子组成的非芳香碳环，并且至少含有一个碳碳三键。环炔基组的例子包括，但不限于，环庚炔基、环辛烯基、cyclonontynyl，以及类似化合物。术语“杂环炔基”是一类上文所定义的环炔基组，并且包括在术语“环炔基”的含义中，其中环上的至少一个碳原子被一杂原子所取代，该杂原子包括但不限于，氮、氧、硫或磷。环炔基组和杂环炔基组可以是取代性的和非取代性的。环炔基组和杂环炔基组可以被一种或多种组取代，包括但不限于，本文所描述的烷基、环烷基、烷氧基,、烯基、环烯基、炔基、环炔基、芳基、杂芳基、乙醛、氨基、羧酸、酯、醚、卤、羟基、酮、叠氮、硝基、甲硅烷基、磺氧基或硫醇。The term "cycloalkynyl" as used herein is a non-aromatic carbocyclic ring consisting of at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctenyl, cyclonontynyl, and the like. The term "heterocycloalkynyl" is a class of cycloalkynyl groups as defined above and is included within the meaning of the term "cycloalkynyl" in which at least one carbon atom of the ring is replaced by a heteroatom, the heteroatom Atoms include, but are not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl groups and heterocycloalkynyl groups may be substituted and unsubstituted. Cycloalkynyl groups and heterocycloalkynyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl as described herein , cycloalkynyl, aryl, heteroaryl, acetaldehyde, amino, carboxylic acid, ester, ether, halo, hydroxyl, ketone, azide, nitro, silyl, sulfoxy, or thiol.

本文所使用的术语“芳基”是一种包含任何碳基芳香组的组，包括但不限于，苯、萘、苯基、联苯、苯氧基苯，及类似化合物。术语“芳基”还包括“杂芳基”，“杂芳基”被定义为一个包含芳香基团的基团，该基团至少有一个包含在芳香基团环中的杂原子。杂原子的例子包括但不限于氮、氧、硫和磷。同样，也包含在术语“芳基”中的术语“非杂芳基”定义了一个包含以芳香基团的基团，而该芳香基团不包含杂原子。芳基组可以是取代性的和非取代性的。芳基组可以被一种或多种组取代，包括但不限于，本文所描述的烷基、环烷基、烷氧基,、烯基、环烯基、炔基、环炔基、芳基、杂芳基、乙醛、氨基、羧酸、酯、醚、卤、羟基、酮、叠氮、硝基、甲硅烷基、磺氧基或硫醇。术语“联芳基”是一种特定类型的芳基组，并且被包括在“芳基”的定义中。联芳基指的是通过一个稠环结构结构连接到一起的两种芳基组，如同萘那样，或者，通过一个或多个碳碳键附着到一起，如同联苯那样。As used herein, the term "aryl" is a group comprising any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and similar compounds. The term "aryl" also includes "heteroaryl", which is defined as an aromatic-containing group having at least one heteroatom contained within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl", also encompassed by the term "aryl", defines a group comprising an aromatic group that does not contain heteroatoms. Aryl groups can be substituted and unsubstituted. Aryl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, as described herein , heteroaryl, acetaldehyde, amino, carboxylic acid, ester, ether, halo, hydroxyl, ketone, azide, nitro, silyl, sulfoxy, or thiol. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together by a fused ring structure, as in naphthalene, or, by one or more carbon-carbon bonds, as in biphenyl.

本文所使用术语“醛”是由分子式—C(O)H所表示的。在本文的整个描述中，“C(O)”是羰基组的一种速记符号，也就是，C＝OThe term "aldehyde" as used herein is represented by the formula -C(O)H. Throughout the description herein, "C(O)" is a shorthand notation for a carbonyl group, that is, C=O

本文所使用的术语“胺”或“氨基”由分子式—NA¹A²表示，其中A¹和A²可以是，独立的，本文所描述的氢或烷基、烯基、环烯基,炔基、环炔基、芳基，或杂芳基组The term "amine" or "amino" as used herein is represented by the formula -NA¹ A² , where A¹ and A² can be, independently, hydrogen or an alkyl, alkenyl, cycloalkenyl, alkyne as described herein group, cycloalkynyl, aryl, or heteroaryl group

本文所使用的术语“烷基氨基”由分子式—NH(-烷基)所表示，其中烷基在本文中得到了描述。有代表性的例子包括，但不限于，甲基氨基组、乙基氨基组、丙基氨基组、异丙基氨基组、丁基氨基组、异丁基氨基组、(仲丁基)氨基组、(叔丁基)氨基组、戊(烷)基氨基组、异戊基氨基组、(叔戊基)氨基组、己基氨基组，及类似化合物。As used herein, the term "alkylamino" is represented by the formula -NH(-alkyl), where alkyl is described herein. Representative examples include, but are not limited to, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, (sec-butyl)amino group , (tert-butyl) amino group, pentyl (alkyl) amino group, isopentyl amino group, (tert-amyl) amino group, hexyl amino group, and similar compounds.

本文所使用的术语“二烷基氨基”由分子式—N(-烷基)₂所表示，其中烷基在本文中得到了描述。有代表性的例子包括，但不限于，二甲基氨基组、二乙基氨基组、二丙基氨基组、二异丙基氨基组、二丁基氨基组、二异丁基氨基组、二(仲丁基)氨基组、二(叔丁基)氨基组、二戊(烷)基氨基组、二异戊基氨基组、二(叔戊基)氨基组、二己基氨基组、N-乙基-N-甲基氨基组、N-甲基-N-丙基氨基组、N-乙基-N-丙基氨基组，及类似化合物。As used herein, the term "dialkylamino" is represented by the formula —N(-alkyl)₂ , where alkyl is described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di (Second-butyl)amino group, di(tert-butyl)amino group, dipentyl (alkyl)amino group, diisoamylamino group, di(tert-amyl)amino group, dihexylamino group, N-ethyl Base-N-methylamino group, N-methyl-N-propylamino group, N-ethyl-N-propylamino group, and similar compounds.

本文所使用的术语“羧酸”由分子式—C(O)OH所表示.The term "carboxylic acid" as used herein is represented by the molecular formula -C(O)OH.

本文所使用的术语“酯”由分子式OC(O)A¹或—C(O)OA¹所表示，其中A¹可以是，本文所述的烷基、环烷基烷基、烯基、环烯基、炔基、环炔基、芳基、杂芳基组。本文所使用的术语“聚酯”由分子式—(A¹O(O)C-A²-C(O)O)_a—或—(A¹O(O)C-A²-OC(O))_a—所表示.，其中，可以A¹和A²是，独立的，本文所描述的一种烷基、环烷基烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基组，并且“a”是一个从1到500的整数。“聚酯”作为术语用于描述由拥有至少两个羧酸组的化合物和拥有至少两个羟基组的化合物进行反应所产生的一种组。The term "ester" as used herein is represented by the formula OC(O)A¹ or —C(O)OA¹ , where A¹ can be, alkyl, cycloalkylalkyl, alkenyl, cyclo Alkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl groups. The term "polyester" as used herein is defined by the formula -(A¹ O(O)CA² -C(O)O)_{a -or} -(A¹ O(O)CA² -OC(O))_a Represents ., wherein,^A and^A can be, independently, an alkyl, cycloalkylalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein basis set, and "a" is an integer from 1 to 500. "Polyester" is a term used to describe a group resulting from the reaction of a compound having at least two carboxylic acid groups with a compound having at least two hydroxyl groups.

本文所使用的术语“醚”由分子式OC(O)A¹所表示，其中A¹和A²可以是，本文所述的烷基、环烷基烷基、烯基、环烯基、炔基、环炔基、芳基、杂芳基组。本文所使用的术语“聚醚”由分子式—(A¹O-A²O)_a—,所表示，其中A¹和A²可以是，独立的，本文所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基、杂芳基组，并且“a”是一个从1到500的整数。聚醚组的例子包括聚乙烯氧化物、聚丙烯氧化物和聚丁烯氧化物。The term "ether" as used herein is represented by the formula OC(O)^A , where^A and^A can be, alkyl, cycloalkylalkyl, alkenyl, cycloalkenyl, alkynyl as described herein , cycloalkynyl, aryl, heteroaryl groups. The term "polyether" as used herein is represented by the formula —(A¹ OA² O)_a —, wherein A¹ and A² can be, independently, alkyl, cycloalkyl, alkenyl as described herein , cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide and polybutene oxide.

术语“聚合的”包括聚亚烃基、聚醚、聚酯和含有重复单元的其它组，包括但不限于，-(CH₂O)_n-CH₃、-(CH₂CH₂O)_n-CH₃、-[CH₂CH(CH₃)]_n-CH₃、-[CH₂CH(COOCH₃)]_n-CH₃、-[CH₂CH(COO CH₂CH₃)]_n-CH₃和-[CH₂CH(COO^tBu)]_n-CH₃，其中n是一个整数(比如，n>1或n>2)。The term "polymeric" includes polyalkylenes, polyethers, polyesters and other groups containing repeating units including, but not limited to, -(CH2O)_n -_CH3 ,_- (_CH2CH2O )_n -_CH3 , -[CH₂ CH(CH₃ )]_n -CH₃ , -[CH₂ CH(COOCH₃ )]_n -CH₃ , -[CH₂ CH(COO CH₂ CH₃ )]_n -CH₃ and -[CH₂ CH(COO^t Bu)]_n -CH₃ , where n is an integer (eg, n>1 or n>2).

本文中使用的术语“卤化物”指的是卤族元素氟、氯、溴和碘。The term "halide" as used herein refers to the halogen elements fluorine, chlorine, bromine and iodine.

本文中使用的术语“杂环基”指的是单和多环非芳香环系统，而本文中使用的“杂芳基”指的是至少一个环系统不是碳的单和多环非芳香环系统。这些术语包括氮杂环丁烷、二氧六环、呋喃、噻唑、咪唑、异恶唑、吗啉、恶唑、吡唑，包括1,2,3-恶二唑,1,2,5-恶二唑和1,3,4-恶二唑，哌嗪、哌啶、吡嗪、吡唑、哒嗪、吡啶、嘧啶、吡咯、吡咯烷酮、四氢呋喃、四氢呋喃、四嗪，包括1,2,4,5-四嗪、四唑，包括1,2,3,4-四唑和1,2,4,5-四唑，噻重氮，包括，1,2,3-噻重氮、1,2,5-噻重氮和1,3,4-噻重氮，噻唑类、噻吩类、三嗪，包括1,3,5-三嗪和1,2,4-三嗪，三唑，包括1,2,3-三唑、1,3,4-三唑和类似化合物。As used herein, the term "heterocyclyl" refers to mono- and polycyclic non-aromatic ring systems, while "heteroaryl" as used herein refers to mono- and polycyclic non-aromatic ring systems in which at least one ring system is not carbon . These terms include azetidine, dioxane, furan, thiazole, imidazole, isoxazole, morpholine, oxazole, pyrazole, including 1,2,3-oxadiazole, 1,2,5- Oxadiazoles and 1,3,4-oxadiazoles, piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidone, tetrahydrofuran, tetrahydrofuran, tetrazine, including 1,2,4 ,5-tetrazine, tetrazole, including 1,2,3,4-tetrazole and 1,2,4,5-tetrazole, thiadiazo, including, 1,2,3-thiadiazo, 1, 2,5-Thiadiazo and 1,3,4-thiadiazo, thiazoles, thiophenes, triazines including 1,3,5-triazine and 1,2,4-triazine, triazoles including 1,2,3-triazole, 1,3,4-triazole and similar compounds.

本文所使用的术语“羟氢氧基”由分子式—OH所表示。As used herein, the term "hydroxyloxy" is represented by the formula —OH.

本文所使用的术语“酮”由分子式A¹C(O)A²所表示，其中A¹和A²可以是，独立的，本文所描述的一种烷基、环烷基烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基组。The term "ketone" as used herein is represented by the formula A¹ C(O)A² , where A¹ and A² can be, independently, an alkyl, cycloalkylalkyl, alkenyl as described herein , cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups.

本文所使用的术语“叠氮化物”由分子式—N₃所表示。The term "azide" as used herein is represented by the formula_—N3 .

本文所使用的术语“硝基”由分子式—NO₂所表示。The term "nitro" as used herein is represented by the formula_-NO2 .

本文所使用的术语“腈”由分子式—CN所表示。The term "nitrile" as used herein is represented by the formula -CN.

本文所使用的术语“甲硅烷基”由分子式—SiA¹A²A³所表示，其中A¹、A²和A³可以是，独立的，本文所描述的一种烷基、环烷基烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基组。The term "silyl" as used herein is represented by the formula - SiA¹ A² A³ , where A¹ , A² and A³ can be, independently, an alkyl, cycloalkylalkane as described herein radical, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group.

本文所使用的术语“氧磺基”由分子式—S(O)A¹，—S(O)₂A¹，—OS(O)₂A¹，或—OS(O)₂OA¹所表示，其中A¹可以是本文所描述的一种烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基组。在本文的描述中，“S(O)”是S＝O的速记简写。本文使用的术语“硫酰”指的是氧磺基，它由由分子式—S(O)₂A¹所表示，其中A¹可以是本文所描述的一种烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基组。本文所使用的术语“砜”由分子式A¹S(O)₂A²所表示，其中A¹和A²可以是，独立的，本文所描述的一种烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基组。本文所使用的术语“亚砜”由分子式A¹S(O)A²所表示，其中A¹和A²可以是，独立的，本文所描述的一种烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基组。The term "oxysulfonyl" used herein is represented by the molecular formula —S(O)A¹ , —S(O)₂ A¹ , —OS(O)₂ A¹ , or —OS(O)₂ OA¹ , wherein^A can be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group described herein. In the description herein, "S(O)" is shorthand for S=O. The term "sulfonyl" as used herein refers to an oxygen sulfo group represented by the molecular formula - S(O)₂ A¹ , where A¹ can be an alkyl, cycloalkyl, alkenyl as described herein , cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups. The term "sulfone" as used herein is represented by the formula A¹ S(O)₂ A² , where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, Cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups. The term "sulfoxide" as used herein is represented by the formula A¹ S(O)A² , where A¹ and A² can be, independently, one of the alkyl, cycloalkyl, alkenyl, Cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups.

本文所使用的术语“硫醇”由分子式—SH所表示。The term "thiol" as used herein is represented by the formula —SH.

本文所使用的“R¹”、“R²”、“R³”和“Rⁿ”(其中n是一个整数)，可以独立地拥有上面所列出的一个或多个组。例如，如果R¹是一个直链烷基组，烷基组的氢原子中的一个可选择性地被一羟氢氧基组、一烷氧基组、一烷基组、一卤化物和类似物质所取代。根据所选的组，第一组可以包含在第二组中，或者，第二种选择是，第一组可以挂到(即附到)第二组上。例如，按照“一种由氨基组组成的烷基组”这种说法，氨基组可包含到烷基组的骨干中。另一种选择是，氨基组可以附着到烷基组的骨干上。所选的组的性质(S)将确定第一组是嵌入还是附着到第二组。"R¹ ", "R² ", "R³ ", and "Rⁿ ", wherein n is an integer, as used herein, may independently possess one or more of the groups listed above. For example, if R is a linear alkyl group,^one of the hydrogen atoms of the alkyl group may optionally be replaced by a hydroxyhydroxy group, an alkoxy group, an alkyl group, a halide and the like Substance replaced. Depending on the group selected, the first group can be contained in the second group, or, alternatively, the first group can hang onto (ie attach to) the second group. For example, in terms of "an alkyl group consisting of amino groups", the amino group may be incorporated into the backbone of the alkyl group. Alternatively, amino groups can be attached to a backbone of alkyl groups. The nature (S) of the selected group will determine whether the first group is embedded or attached to the second group.

本文所述化合物可能含有“选择性取代的”成分。一般来说，无论是否之前附加有“选择性”这个术语，“取代”这个术语意味着指定成分的一个或多个氢被一个合适的取代基所取代。除非另有说明，一“选择性取代”组可能在组的每一个可替代位置拥有一个合适的取代基，如果在任何给定结构中有多个位置可以被从特定组中选择的数目超过一个的取代基所取代，那么该取代基在每一个位置都可以是相同或不同的。组的取代基最好是能够引起形成稳定或化学上可行化合物的那些取代基。也考虑到的是，在某些方面，除非有明确相反的说明，单个取代基可以被进一步选择性取代(即，进一步被取代或未被取代)。The compounds described herein may contain "optionally substituted" components. In general, the term "substituted", whether or not preceded by the term "optionally", means that one or more hydrogens of the indicated component are replaced by a suitable substituent. Unless otherwise stated, an "optionally substituted" group may have a suitable substituent at each alternative position of the group, if more than one of the positions in any given structure can be selected from a particular group substituted by a substituent, the substituent may be the same or different at each position. Groups of substituents are preferably those that result in the formation of stable or chemically feasible compounds. It is also contemplated that in certain aspects, unless expressly stated to the contrary, individual substituents may be further selectively substituted (ie, further substituted or unsubstituted).

在一些方面，一种化合物的结构可以用下面的分子式表示：In some aspects, the structure of a compound can be represented by the following molecular formula:

这种分子式被理解为与下面的分子式相同：This formula is understood to be the same as the following formula:

其中n通常代表一个整数。也就是说，Rⁿ被理解为代表五种独立的取代基，R^n(a)，R^n(b)，R^n(c)，R^n(d)，R^n(e)。“独立取代基”的意思是每个R取代基都能够被独立定义。例如，如果在一个具体实施例中R^n(a)是卤素，那么R^n(b)在那个具体实施例中不一定是卤素。where n usually represents an integer. That is,^Rn is understood to represent five independent substituents, Rn^(a) ,^Rn(b) , Rn^(c) , Rn^(d) , Rn^(e) . "Independent substituents" means that each R substituent can be independently defined. For example, if^Rn(a) is halo in one particular embodiment, then Rn^(b) need not be halo in that particular embodiment.

在本文公开和描述的化学结构和成分中对R，R¹，R²，R³，R⁴，R⁵，R⁶等提到了好几次。在详述中对R，R¹，R²，R³，R⁴，R⁵，R⁶等进行的任何描述都适用于各自对R，R¹，R²，R³，R⁴，R⁵，R⁶等进行描述的任何结构或成分。R, R1, R2,^R3 ,^R4 ,^R5 ,^R6 ,^etc. are mentioned several times in the chemical structures and compositions disclosed and described herein^. Any description of R, R¹ , R² , R³ , R⁴ , R⁵ , R⁶ etc. in the detailed description applies to each of R, R¹ , R² , R³ , R⁴ , R⁵ , R⁶ etc. for any structure or composition described.

利用有机材料的光电器器件正变得越来越受欢迎，而它们受欢迎的原因有很多。用于制造这种器件的许多材料相对便宜，因此有机光电器件相对于无机器件具有潜在的成本优势。此外，有机材料的固有特性，如其柔韧性，可能使它们非常适合于一些特殊应用，如柔性衬底上的加工。有机光电器器件的例子包括有机发光器件(OLED)，有机晶体管，有机太阳能电池和有机光电探测器。对于OLED来说，有机材料相比传统材料可能有性能上的优势。例如，有机发光层发光的波长通常可以很容易用适当的掺杂剂进行调整。Optoelectronic devices utilizing organic materials are becoming increasingly popular, and there are many reasons for their popularity. Many of the materials used to make such devices are relatively inexpensive, so organic optoelectronic devices have a potential cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for some specialized applications, such as processing on flexible substrates. Examples of organic optoelectronic devices include organic light emitting devices (OLEDs), organic transistors, organic solar cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over traditional materials. For example, the wavelength at which an organic light-emitting layer emits light can often be easily tuned with appropriate dopants.

激子从单重激发态到基态的衰减产生冷光，即荧光。激子从三重激发态到基态的衰减产生冷光，即磷光。由于重金属原子的强自旋轨道耦合能非常有效地增强单重激发态和三重激发态之间的系统间交叉(ISC)，磷光金属络合物，如铂络合物，已显示了它们收获单重和三重激发态两者以及达到100％内部量子效率的潜力。因此，磷光金属络合物是作为有机发光器件(OLED)发光层掺杂物的很好候选材料，它在学术和工业领域都以得到非常多的注意。并且在过去的十年中，人们已经在该技术走向高利润商业化的道路上取得了一定成果，例如，OLED已经在智能手机、电视机和数码相机的先进显示器中得到应用。The decay of excitons from the singlet excited state to the ground state produces luminescence, i.e. fluorescence. The decay of the excitons from the triplet excited state to the ground state produces luminescence, or phosphorescence. Since the strong spin-orbit coupling of heavy metal atoms can very effectively enhance the intersystem crossing (ISC) between singlet and triplet excited states, phosphorescent metal complexes, such as platinum complexes, have been shown to harvest singlet Both heavy and triplet excited states and the potential to reach 100% internal quantum efficiency. Therefore, phosphorescent metal complexes are good candidates as dopants for the light-emitting layer of organic light-emitting devices (OLEDs), and they have received a lot of attention in both academic and industrial fields. And in the past decade, some progress has been made on the road to high-profit commercialization of this technology. For example, OLED has been used in advanced displays of smartphones, TVs and digital cameras.

然而，到目前为止，蓝色电致发光器件仍然是这项技术中最具挑战性的领域，原因至少部分是蓝色器件的不稳定性。一般认为，基质材料的选择是影响蓝色器件稳定性的一个因素。但是，蓝色荧光材料的最低三重态激发态(T₁)的能量很高，这一般意味着蓝色器件的基质材料的最低三重态激发态(T₁)能量应该更高。这就给开发蓝色器件基质材料带来了困难。However, blue electroluminescent devices remain by far the most challenging area of the technology, at least in part due to the instability of blue devices. It is generally believed that the choice of host material is a factor affecting the stability of blue devices. However, the energy of the lowest triplet excited state (T₁ ) of the blue fluorescent material is high, which generally means that the energy of the lowest triplet excited state (T₁ ) of the host material of the blue device should be higher. This brings difficulties to the development of blue device host materials.

本发明通过将氘原子(s)引入铂络合物的配体提供了一种材料设计路线。由于氘原子比氢原子重，与C-H键相比，碳-氘(C-D)键的振动可以减少。因此，发射光谱的振动带将减少或削弱，而整个光谱可以变窄。这将能够促进发射光色并改善器件的性能。The present invention provides a material design route by introducing deuterium atom(s) into the ligands of platinum complexes. Since a deuterium atom is heavier than a hydrogen atom, the vibration of a carbon-deuterium (C-D) bond can be reduced compared to a C-H bond. Consequently, the vibrational bands of the emission spectrum will be reduced or weakened, and the entire spectrum can be narrowed. This would be able to boost the color of the emitted light and improve the performance of the device.

这里描述的金属络合物可以被定制或调整以适应需要特定发射或吸收特性的特定应用。本发明中的金属络合物的光学性质可以通过改变围绕金属中心的配体的结构或通过改变配体上荧光发光体(s)的结构而进行调整。例如，具有携带电子供体取代基或电子吸收取代基的配体的金属络合物通常具有不同的光学性质，包括发射和吸收光谱。金属络合物的颜色可以通过更改荧光发光体和配体上的共轭基团而得到调整。The metal complexes described here can be tailored or tuned for specific applications requiring specific emission or absorption properties. The optical properties of the metal complexes in the present invention can be tuned by changing the structure of the ligand surrounding the metal center or by changing the structure of the fluorescent emitter(s) on the ligand. For example, metal complexes with ligands bearing electron-donating substituents or electron-absorbing substituents often have different optical properties, including emission and absorption spectra. The color of metal complexes can be tuned by changing the conjugated groups on the fluorescent emitters and ligands.

这种复合物的发射可以通过，比如，修改配体或荧光发光体的结构，而调整(例如，从紫外到近红外)。荧光发光体是一有机分子中的一组原子，该原子可以吸收能量从而产生单重激发态。该单重激发子能产生衰减从而迅速产生及时冷光。一方面，该络合物可以在大部分的可见光谱上发光。在具体的例子中，本文描述的络合物可以在从400纳米到700纳米的范围内发光。另一方面，络合物提高了传统发射络合物的稳定性和效率。再一方面，所述络合物可用作为，比如，生物应用、抗癌剂、有机发光二极管(OLED)中的发射器或其组合，的发光标签。最后一方面，络合物可用于发光器件，例如，紧凑型荧光灯(CFL)、发光二极管(LED)和白炽灯等。The emission of such complexes can be tuned (eg, from ultraviolet to near infrared) by, for example, modifying the structure of the ligand or fluorescent emitter. A fluorescent emitter is a group of atoms in an organic molecule that absorbs energy to produce a singlet excited state. The singlet excitons can be decayed to rapidly produce timely luminescence. On the one hand, the complex can emit light over most of the visible spectrum. In specific examples, the complexes described herein can emit light in the range from 400 nanometers to 700 nanometers. On the other hand, the complex improves the stability and efficiency of conventional emissive complexes. In yet another aspect, the complexes can be used as luminescent labels, for example, for biological applications, anticancer agents, emitters in organic light emitting diodes (OLEDs), or combinations thereof. In a final aspect, the complexes are useful in light emitting devices such as compact fluorescent lamps (CFLs), light emitting diodes (LEDs), and incandescent lamps, among others.

本文公开了含有铂、钯或金的化合物或化合物络合物。术语化合物、化合物络合物和络合物在本文中得到了交替使用。一方面，本文公开的化合物具有中性电荷。Compounds or compound complexes containing platinum, palladium or gold are disclosed herein. The terms compound, compound complex and complex are used interchangeably herein. In one aspect, the compounds disclosed herein have a neutral charge.

本发明公开的化合物可以表现出理想的性质，并且具有可以通过选择适当配体来调整的发射和/或吸收光谱。另一方面，在本文中得到特别描述的它们的化合物、结构或部分的任何一个或任何多个可能会被排除在外。The compounds disclosed herein can exhibit desirable properties and have emission and/or absorption spectra that can be tuned by selection of appropriate ligands. On the other hand, any one or any number of their compounds, structures or moieties specifically described herein may be excluded.

本文所公开的化合物适用于各种光学和光电器件，包括，但不限于，诸如太阳能和光敏感器件之类光吸收器件、有机发光二极管(OLED)、光发射器件或既有光吸收又有光发射能力的器件以及用于生物应用的标志物。The compounds disclosed herein are useful in a variety of optical and optoelectronic devices including, but not limited to, light absorbing devices such as solar and light sensitive devices, organic light emitting diodes (OLEDs), light emitting devices or both light absorbing and light emitting devices capable devices and markers for biological applications.

如上文简单叙述，所公开的化合物是铂络合物。一方面，本文公开的化合物可以用作OLED应用，如全彩显示器，的基质材料。As briefly stated above, the disclosed compounds are platinum complexes. In one aspect, the compounds disclosed herein can be used as matrix materials for OLED applications, such as full color displays.

本文公开的化合物在各种应用中都有使用价值。作为发光材料，这些化合物可用于有机发光二极管(OLED)、发光器件和显示器以及其它发光器件。The compounds disclosed herein find use in a variety of applications. As light-emitting materials, these compounds are useful in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

另一方面，这些化合物可以在照明器件，例如，有机发光器件中，提供比传统材料更好的效率和/或使用寿命。On the other hand, these compounds may provide better efficiency and/or lifetime than conventional materials in lighting devices, eg, organic light emitting devices.

本文中所描述的化合物可以使用多种方法制成，包括，但不限于，示例中所描述的那些。The compounds described herein can be made using a variety of methods, including, but not limited to, those described in the Examples.

本文公开的化合物包括延迟荧光发射体、磷光发射体或它们的组合。一方面，本文公开的化合物是延迟荧光发射器。另一方面，本文公开的化合物是磷光发射体。再另一方面，本文公开的一化合物是一延迟荧光发射体和一磷光发射体两者。The compounds disclosed herein include delayed fluorescent emitters, phosphorescent emitters, or combinations thereof. In one aspect, the compounds disclosed herein are delayed fluorescence emitters. In another aspect, the compounds disclosed herein are phosphorescent emitters. In yet another aspect, a compound disclosed herein is both a delayed fluorescence emitter and a phosphorescent emitter.

此处公开的是1型分子式络合物：Disclosed here is a type 1 complex of formula:

R^a代表单、双、三或四基取代，R^a是独立的氘，CDH₂，CD₂H，CD₃，CD R¹R²，CD₂R¹，或其他含氘的烷基芳、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单取代氨基、二烃基氨基、单氨基、二芳基胺、烷氧基、芳氧基、卤代基、芳烷基、酯、烷氧羰基、酰胺基、烷氧基羰基氨基，烷氧基碳酰基氨基、芳氧基碳酰基氨基、芳烷基、氨磺酰、氨基甲酰基、烷硫基，脲基、磷酰胺、甲硅烷基、聚合物；或其任何结合物或化合物。R^a represents mono-, di-, tri- or tetra-substitution, R^a is independent deuterium, CDH₂ , CD₂ H, CD₃ , CD R¹ R² , CD₂ R¹ , or other deuterium-containing alkyl aromatics, Cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monosubstituted amino, dihydrocarbylamino, monoamino, diarylamine, alkoxy, aryloxy , halo, aralkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aralkyl, sulfamoyl, carbamoyl, Alkylthio, ureido, phosphoramide, silyl, polymer; or any combination or compound thereof.

R^b、R^c、R^d和R^e中的每一种都是要么独立存在的或不存在的，如果是存在的，那么R^b、R^c、R^d和R^e中的每一种分别代表单或双基取代，R^b,R^d和R^e也可以是三基取代，R^b可以是四基取代，并且其中R^b、R^c、R^d和R^e中的每一种是独立的氘、卤素、羟基、巯基、硝基、氰基、腈、异腈、亚磺酰基、巯基、磺基、羧基、肼基；取代或未取代的：芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤代烷基、芳烷基、酯、烷氧基羰基、酰基氨基、烷氧基羰基氨基、芳基含氧羰基氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物，R^a和R^b可选择性地连接形成熔合环，R^d和R^e可选择性地连接形成熔合环。Each of R^b , R^c , R^d and^Re is either independently present or absent, and if present, each of R^b , R^c , R^d and^Re respectively Represents single or double substitution, R^b , R^d and^Re may also be tri-substitution, R^b may be tetra-substitution, and each of R^b , R^c , R^d and^Re is independently Deuterium, halogen, hydroxyl, mercapto, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl , heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl , aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, sulfonamide, carbamoyl, alkylthio, ureido, phosphoramide, Silyl, polymerization; or any combination or compound thereof, R^a and R^b may be optionally connected to form a fused ring, R^d and^Re may be optionally connected to form a fused ring.

R¹和R²中的每一种都是独立的氢、氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、氧芳基、卤烷基、芳烷基,、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、硫烷基、脲基、磷酰胺、甲硅烷基、聚合物；或其任何结合物或化合物。Each^of R and R is independently^hydrogen , deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternative or irreplaceable: aryl, cycloalkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkyl Amino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, Aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, sulfanyl, ureido, phosphoramide, silyl, polymer; or any combination or compound thereof.

一方面，该铂络合物具有分子式2、分子式3、分子式4、分子式5、分子式6或分子式7的结构。另一方面，它们也可以包含其在这儿没有得到专门详述的其他结构或部分，本发明不应局限于其那些在此得到专门详述的结构或部分。In one aspect, the platinum complex has the structure of formula 2, formula 3, formula 4, formula 5, formula 6 or formula 7. On the other hand, they may also contain other structures or parts thereof that are not specifically described in detail here, and the present invention should not be limited to those structures or parts thereof that are specifically described in detail here.

R^b、R^c、R^d和R^e中的每一种都是要么独立存在的或不存在的，如果是存在的，那么R^b、R^c、R^d和R^e中的每一种分别代表单或双基取代，R^b,R^d和R^e也可以是三基取代，R^b可以是四基取代，并且其中R^b、R^c、R^d和R^e中的每一种是独立的氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；替代或不替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物，R^a和R^b可选择性地连接形成熔合环，R^d和R^e可选择性地连接形成熔合环。Each of R^b , R^c , R^d and^Re is either independently present or absent, and if present, each of R^b , R^c , R^d and^Re respectively Represents single or double substitution, R^b , R^d and^Re may also be tri-substitution, R^b may be tetra-substitution, and each of R^b , R^c , R^d and^Re is independently deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternatively or not: aryl, cyclic Alkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino , alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, sulfonamide, carbamoyl, alkane Thio group, ureido group, phosphoramidite, silyl group, polymerization; or any combination or compound thereof, R^a and R^b can be optionally linked to form a fusion ring, R^d and R^e can be optionally linked to form a fusion ring .

R¹和R²中的每一种都是独立的氢、氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基、环环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物。Each^of R and R is independently^hydrogen , deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, Carboxyl, hydrazino; alternative or irreplaceable: aryl, cycloalkyl, cyclocycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dioxane arylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfur Amylamino, sulfonamide, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any combination or compound thereof.

对于本文中描述的分子式1至4，它的群类可能在下文的描述中得到定义。For formulas 1 to 4 described herein, its group may be defined in the description below.

一方面，R^a是单取代。另一方面，R^a是双取代。再另一方面，R^a是三取代。最后一方面，R^a是四取代。In one aspect,^Ra is monosubstituted. In another aspect, R^a is disubstituted. In yet another aspect,^Ra is trisubstituted. In a final aspect, R^a is tetrasubstituted.

一方面，R^a是独立氘,CDH₂，CD₂H，CD₃，CD R¹R²，CD₂R¹，或其它含氘烷芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、双烷基氨基、单芳基氨基、双芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物。In one aspect, R^a is independently deuterium, CDH₂ , CD₂ H, CD₃ , CD R¹ R² , CD₂ R¹ , or other deuterium-containing alkaryl, cycloalkylalkyl, cycloalkenylcycloalkenyl , heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, bisarylamino, alkoxy, aryloxy, haloalkane group, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, alkylthio, ureido, phosphoramide, formazan silyl, polymeric; or any combination or compound thereof.

一方面，一种R^b是存在的。另一方面，R^b是不存在的。In one aspect, an^Rb is present. On the other hand, R^b is absent.

一方面，R^b是单取代。另一方面，R^b是双取代。再另一方面，R^b是三取代。最后一方面，R^b是四取代。In one aspect,^Rb is monosubstituted. In another aspect,^Rb is disubstituted. In yet another aspect,^Rb is trisubstituted. In a final aspect,^Rb is tetrasubstituted.

一方面，每一^种R^b都是独立氘、卤^素、羟氢氧基、硫醇、硝基、^氰基、腈、异腈、亚硫酰基、^氢硫基、磺基、羧基、肼基；可^代替的或不科代替的：芳基、环烷基、环环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰基氨基、烷氧基羰基氨基、芳氧基羰基氨基、硫酰氨基、氨磺酰、氨基甲酰、硫烷基、脲基、磷酰胺、甲硅烷基,聚合的；或其任何结合物或化合物。In^one aspect, each R is independently^deuterium ,^halogen ,^{hydroxyhydroxyl} , mercaptan, nitro,^cyano , nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino ;^Alternative or irreplaceable: aryl, cycloalkyl, cyclocycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkyl Amino, monoarylamino, arylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonyl Amino, sulfonyl, carbamoyl, sulfanyl, ureido, phosphoramide, silyl, polymeric; or any combination or compound thereof.

一方面，一种Rc是存在的。另一方面，Rc是不存在的。In one aspect, an Rc is present. Rc, on the other hand, does not exist.

一方面，Rc是单取代。另一方面，Rc是双取代。In one aspect, Rc is a mono substitution. In another aspect, Rc is a double substitution.

一方面，每一种R^c都是独立的氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物。In one aspect, each^Rc is independently deuterium, halo, hydroxyhydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino ;Alternative or irreplaceable: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoaryl Alkylamino, diarylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamo acyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any combination or compound thereof.

一方面，一种R^d是存在的。另一方面，R^d是不存在的。In one aspect, an^Rd is present. On the other hand,^Rd is absent.

一方面，R^d是单取代。另一方面，R^d是双取代。再另一方面，R^d是三取代。In one aspect,^Rd is monosubstituted. In another aspect,^Rd is disubstituted. In yet another aspect, R^d is trisubstituted.

一方面，每一种R^d都是独立的氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物。In one aspect, each^Rd is independently deuterium, halogen, hydroxyhydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino ;Alternative or irreplaceable: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoaryl Alkylamino, diarylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamo acyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any combination or compound thereof.

一方面，一种R^e是存在的。另一方面，R^e是不存在的。In one aspect, a^Re is present.^Re , on the other hand, does not exist.

一方面，R^e是单取代。另一方面，R^e是双取代。再另一方面，R^e是三取代。In one aspect, R^e is a mono substitution. In another aspect, R^e is a double substitution. In yet another aspect,^Re is trisubstituted.

一方面，每一种R^e都是独立的氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物。In one aspect, each R is independently^deuterium , halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino ;Alternative or irreplaceable: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoaryl Alkylamino, diarylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamo acyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any combination or compound thereof.

一方面，R、R1和R2中的每一种都是独立的氢、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、双烷基氨基、单芳基氨基、双芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰基氨基、烷氧基羰基氨基、芳氧基羰基氨基、硫酰氨基、氨磺酰、氨基甲酰、硫烷基、脲基、磷酰胺、可替代甲硅烷基、聚合，或,或其任何结合物或化合物。零一方面，R、R1和R2中的每一种都是独立的氢、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟氢氧基、硫醇、硝基、氰基或氨基.再一方面，R、R1和R2中的每一种都是独立的氢、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基或炔基。In one aspect, each of R, R1, and R2 is independently hydrogen, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo , carboxyl, hydrazino, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino , bisarylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, sulfonamide , carbamoyl, sulfanyl, ureido, phosphoramide, alternative silyl, polymeric, or, or any combination or compound thereof. In one aspect, each of R, R1 and R2 is independently hydrogen, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, Hydroxyhydroxyl, thiol, nitro, cyano or amino. In another aspect, each of R, R1 and R2 is independently hydrogen, aryl, cycloalkyl, cycloalkenyl, heterocyclyl , heteroaryl, alkyl, alkenyl or alkynyl.

一方面，对于本文公开的任一种分子式，是下列结构中独立的一种。另一方面，它们还可以包括它们的未在本文中得到具体叙述的其他结构或部分，并且本发明没有意图仅限于它们的那些得到特别叙述的结构或部分。In one aspect, for any molecular formula disclosed herein, is an independent one of the following structures. On the other hand, they may also include other structures or parts thereof which are not specifically recited herein, and the present invention is not intended to be limited to those structures or parts thereof which are specifically recited.

二、示例性化合物2. Exemplary compounds

一方面，本发明的公开内容所说明的金属络合物可包含以下一或多个结构。另一方面，它们也可包含本文未明确述及的其他结构或这些结构之部分，而并不意旨将本发明的公开内容限制于明确述及的该等结构或其部分。In one aspect, the metal complexes described in the present disclosure may comprise one or more of the following structures. On the other hand, they may also include other structures or parts of these structures not explicitly mentioned herein, and it is not intended to limit the disclosure of the present invention to these structures or parts thereof explicitly mentioned.

本文还公开了包括本文所公开化合物中的一或多种的器件。Also disclosed herein are devices comprising one or more of the compounds disclosed herein.

本文所公开的化合物适用于各种光学和光电器件，包括，但不限于，诸如太阳能和光敏感器件这样的光吸收器件、有机发光二极管(OLED)、光发射器件或既有光吸收又有光发射能力的器件以及用于生物应用的标志物。The compounds disclosed herein are suitable for use in a variety of optical and optoelectronic devices including, but not limited to, light absorbing devices such as solar and light sensitive devices, organic light emitting diodes (OLEDs), light emitting devices or both light absorbing and light emitting devices capable devices and markers for biological applications.

本文所说明的化合物可用在一种诸如OLED之类的发光器件中。图1说明了OLED1000的断面图。OLED 1000包括基体1002、阳级1004、空穴传输材料(HTL)1006、光处理材料1008、电子传输材料(ETL)1010及一金属阴极层1012。阳极1004一般是透明材料，例如氧化铟锡。光处理材料1008可以是包括一发射体和一主体的发光材料(EML)。The compounds described herein can be used in a light emitting device such as an OLED. FIG. 1 illustrates a cross-sectional view of OLED 1000 . OLED 1000 includes substrate 1002 , anode 1004 , hole transport material (HTL) 1006 , light processing material 1008 , electron transport material (ETL) 1010 and a metal cathode layer 1012 . The anode 1004 is generally a transparent material such as indium tin oxide. The light-manipulating material 1008 may be an emissive material (EML) that includes an emitter and a host.

图1显示OLED 1000的断面图，其包括：具有一阳极1004的基体1002，一般是透明材料，例如氧化铟锡，；一空穴传输材料层(HTL)1006；一发光功能材料1008，例如包括一发射体和一主体的发光材料；一电子传输材料层(ETL)1010及一金属阴极层1012。一方面，诸如OLED之类的发光器件可包含一或多层。从各方面说，该一或该等多层的任何层均可包含氧化铟锡(ITO)、MoO₃、Ni₂O₃、聚(3,4-乙烯二氧噻吩)(PEDOT)、聚苯乙烯磺酸钠(PSS)、4,4',4”-((1E,1'E,1”E)-环丙烷-1,2,3-三亚甲基三(氰基-甲基亚基))三(2,3,5,6-四氟苯腈)(NHT-49)、2,2'-(全氟萘烷-2,6-二基)丙二腈(NHT-51)、2,3,5,6-四氟四氰基-对醌二甲烷(F4-TCNQ)、N,N′-二-1-萘基-N,N′-联苯-1,1′-联苯-4,4′二胺(NPD)、1,1-顺((二-4-对甲苯氨基)苯基)环己烷(TAPC),2,6-顺(N-咔唑基)-吡啶(mCpy)、2,8-顺(叠氮磷酸二苯酯)二苯并噻吩(PO15)、LiF、LiQ、Cs₂CO₃、CaCO₃、Al或其组合物。在这一具体实施方式中，光处理材料层1008可包含本发明的一或多个化合物，可选择性地连带一主体材料。ETL层1010和1006还可包含一或多个化合物以及与电极接近的另一注入层。注入层的材料可包括(电子注入层)EIL、(空穴注入层)HIL和CPL(盖层)，其形式可以是单一层或分散在传输材料中。主体材料可以是本技术中已知的任何合适的主体材料。OLED的发光颜色由光处理材料1008的发光能量(光学能隙)决定，可如上所述通过调谐发射化合物和/或主体材料的电子结构来调谐光处理材料1008的发光能量(光学能隙)。HTL层1006中的空穴传输材料和ETL层1010中的电子传输材料可包含本技术中已知的任何合适的空穴传输体。对此的选择属于熟悉本技术者的权限范围。1 shows a cross-sectional view of an OLED 1000, which includes: a substrate 1002 with an anode 1004, generally a transparent material, such as indium tin oxide; a hole transport material layer (HTL) 1006; a light-emitting functional material 1008, for example including a Emitter and a host luminescent material; an electron transport material layer (ETL) 1010 and a metal cathode layer 1012 . In one aspect, a light emitting device such as an OLED can comprise one or more layers. In all aspects, the one or any of the layers may comprise indium tin oxide (ITO), MoO₃ , Ni₂ O₃ , poly(3,4-ethylenedioxythiophene) (PEDOT), polyphenylene Sodium ethylene sulfonate (PSS), 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyano-methylidene) )) Tris(2,3,5,6-tetrafluorobenzonitrile) (NHT-49), 2,2'-(perfluorodecalin-2,6-diyl) malononitrile (NHT-51), 2,3,5,6-Tetrafluorotetracyano-p-quinodimethane (F4-TCNQ), N,N'-di-1-naphthyl-N,N'-biphenyl-1,1'-bi Benzene-4,4′diamine (NPD), 1,1-cis((di-4-p-tolylamino)phenyl)cyclohexane (TAPC), 2,6-cis(N-carbazolyl)- Pyridine (mCpy), 2,8-cis(diphenylphosphoryl azido)dibenzothiophene (_PO15 ), LiF,_LiQ ,_Cs2CO3 , CaCO3, Al, or combinations thereof. In this embodiment, the light-management material layer 1008 may comprise one or more compounds of the present invention, optionally together with a host material. The ETL layers 1010 and 1006 may also include one or more compounds and another injection layer proximate to the electrodes. Materials for the injection layer may include (electron injection layer) EIL, (hole injection layer) HIL, and CPL (capping layer), which may be in the form of a single layer or dispersed in a transport material. The host material may be any suitable host material known in the art. The emission color of the OLED is determined by the emission energy (optical energy gap) of the light processing material 1008, which can be tuned by tuning the electronic structure of the emissive compound and/or the host material as described above. The hole transport material in HTL layer 1006 and the electron transport material in ETL layer 1010 may comprise any suitable hole transporter known in the art. The choice of this is within the purview of those skilled in the art.

显然，本发明的化合物可呈现磷光。磷光OLED(即，具有磷光发射体的OLED)一般具有比诸如荧光OLED之类的其他OLED更高的器件效率。在《自然》1998年395期第151-154页说明了基于电致磷光发射体的发光器件，因其关于OLED而尤其是关于荧光OLED的讲授内容，以引用的方式并入于此。Apparently, the compounds of the present invention can exhibit phosphorescence. Phosphorescent OLEDs (ie, OLEDs with phosphorescent emitters) generally have higher device efficiencies than other OLEDs, such as fluorescent OLEDs. Light emitting devices based on electrophosphorescent emitters are described in Nature 1998 395, pp. 151-154, which is hereby incorporated by reference for its teaching on OLEDs, and in particular fluorescent OLEDs.

从各方面说，图1所说明的一或多层中的任何层均可包括氧化铟锡(ITO)、MoO3、Ni2O3、聚(3,4-乙烯二氧噻吩)(PEDOT)、聚苯乙烯磺酸钠(PSS)、N,N′-二-1-萘基-N,N′-联苯-1,1′-联苯-4,4′二胺(NPD)、1,1-顺((二-4-对甲苯氨基)苯基)环己烷(TAPC)、2,6-顺(N-咔唑基)-吡啶(mCpy)、2,8-顺(叠氮磷酸二苯酯)二苯并噻吩(PO15)、LiF、Al或其组合物。In all respects, any of the one or more layers illustrated in Figure 1 may include indium tin oxide (ITO), MoO3, Ni2O3, poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene Sodium sulfonate (PSS), N,N'-di-1-naphthyl-N,N'-biphenyl-1,1'-biphenyl-4,4'diamine (NPD), 1,1-cis ((Di-4-p-tolylamino)phenyl)cyclohexane (TAPC), 2,6-cis(N-carbazolyl)-pyridine (mCpy), 2,8-cis(diphenylphosphorylazide ) dibenzothiophene (PO15), LiF, Al or combinations thereof.

光处理层1008可包括本发明的一或多个化合物，可选择性地连带一主体材料。主体材料可以是本技术中已知的任何合适的主体材料。OLED的发光颜色由光处理材料1008的发光能量(光学能隙)决定，可通过调谐发射化合物、主体材料或两者的电子结构来调谐光处理材料1008的发光能量(光学能隙)。HTL层1006中的空穴传输材料和ETL层1010中的电子传输材料可包括本技术中已知的任何合适的空穴传输体。Photo-management layer 1008 may include one or more compounds of the present invention, optionally together with a host material. The host material may be any suitable host material known in the art. The luminous color of OLED is determined by the luminous energy (optical energy gap) of the light processing material 1008, which can be tuned by tuning the electronic structure of the emissive compound, the host material or both. The hole transport material in HTL layer 1006 and the electron transport material in ETL layer 1010 may comprise any suitable hole transporter known in the art.

本文所说明的化合物可呈现磷光。磷光OLED(即，具有磷光发射体的OLED)一般具有比诸如荧光OLED之类的其他OLED更高的器件效率。在WO2000/070655中更详细地说明了基于电致磷光发射体的发光器件，因其关于OLED而尤其是关于荧光OLED的讲授内容，以引用的方式并入于此。The compounds described herein can exhibit phosphorescence. Phosphorescent OLEDs (ie, OLEDs with phosphorescent emitters) generally have higher device efficiencies than other OLEDs, such as fluorescent OLEDs. Light emitting devices based on electrophosphorescent emitters are described in more detail in WO2000/070655, which is hereby incorporated by reference for its teaching on OLEDs, and in particular fluorescent OLEDs.

以下示例的提出是为了向所属领域的技术人员完整地公开和说明对于本文所要求保护的化合物、组成物、物件、器件和/或方法是如何制作并评估的，并且意旨纯为示例性而并非作范围限制。已尽力确保在数字方面的精确性(例如，数量、温度等)，但是对于一些误差和偏差应加以考虑。除另有指示外，部件是按重量而论的部件，温度是以℃为单位或者是环境温度，而压力是处于或接近大气压。The following examples are presented to fully disclose and illustrate to those skilled in the art how to make and evaluate the compounds, compositions, objects, devices and/or methods claimed herein, and are intended to be purely exemplary and not intended to limit the scope. Efforts have been made to ensure numerical accuracy (eg, amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.

本文所说明的化合物的各种制备方法是以示例来讲述。所提供的这些方法是用于说明各种制备方法，但是其意旨并非限制本文所述的任何方法。相应地，对本发明的公开内容拥有所有权的本领域技术人员可以方便地修改所述方法或者采用不同方法来制备本文所说明的化合物中的一或多种。以下方面仅作为示例，而其意旨并非作范围限制。温度、催化剂、浓度、反应物组成及其他工艺条件可以变化，而对本发明的公开内容拥有所有权的本领域技术人员可针对所需络合物来方便地选择适当的反应物和条件。The various methods of preparation of the compounds described herein are taught by way of example. These methods are provided to illustrate various methods of preparation, but are not intended to limit any method described herein. Accordingly, one of skill in the art having ownership of the present disclosure can readily modify the methods described or employ a different method to prepare one or more of the compounds described herein. The following aspects are examples only and are not intended to be limiting in scope. Temperatures, catalysts, concentrations, reactant compositions, and other process conditions can be varied, and one skilled in the art having ownership of this disclosure can readily select appropriate reactants and conditions for the desired complex.

在CDCl₃或DMSO-d₆溶液中，通过Varian液态核磁共振仪记录¹H NMR(氢核磁共振)和¹³C NMR(碳核磁共振)光谱为300、400或500MHz，而化学位移是以残余的质子化溶剂为基准。如果使用CDCl₃作为溶剂，则采用四甲基硅烷(δ＝0.00ppm)作为内参比来记录¹H NMR(氢核磁共振)光谱；采用CDCl₃(δ＝77.00ppm)作为内参比来记录¹³C NMR(碳核磁共振)光谱。如果使用DMSO-d⁶作为溶剂，则采用残余的H₂O(δ＝3.33ppm)作为内参比来记录¹H NMR(氢核磁共振)光谱；采用DMSO-d⁶(δ＝39.52ppm)作为内参比来记录¹³C NMR(碳核磁共振)光谱。以下缩写词(或其组合)是用于解说¹H NMR(氢核磁共振)的多样性：s＝单线态，d＝双线态，t＝三线态，q＝四线态，p＝五线态，m＝多线态，br＝宽。¹ H NMR (hydrogen nuclear magnetic resonance) and¹³ C NMR (carbon nuclear magnetic resonance) spectra were recorded by a Varian liquid-state NMR instrument at 300, 400 or 500 MHz in CDCl₃ or DMSO-d₆ solution, and the chemical shifts were expressed as residual Protonated solvents were used as benchmarks. If using_CDCl3 as solvent, record¹ H NMR (hydrogen nuclear magnetic resonance) spectra using tetramethylsilane (δ = 0.00 ppm) as internal reference; record¹³ C using CDCl₃ (δ = 77.00 ppm) as internal reference NMR (carbon nuclear magnetic resonance) spectroscopy. If DMSO-d⁶ is used as solvent, use residual H₂ O (δ=3.33ppm) as internal reference to record¹ H NMR (hydrogen nuclear magnetic resonance) spectrum; use DMSO-d⁶ (δ=39.52ppm) as internal reference¹³ C NMR (Carbon Nuclear Magnetic Resonance) spectra were then recorded. The following abbreviations (or combinations thereof) are used to illustrate the diversity of¹ H NMR (hydrogen nuclear magnetic resonance): s = singlet, d = doublet, t = triplet, q = quadruplet, p = pentagent state, m=multit, br=broad.

铂络合物1是按照以下方案制备：Platinum complex 1 was prepared according to the following scheme:

2-溴-4-D-吡啶的合成：向一个100mL的烧瓶添加2,6-二溴吡啶(2.36g，10mmol)，在室温下溶解于新鲜蒸馏的四氢呋喃(THF)中。然后逐滴添加i-PrMgBr(8mL，12.8mmol)的正乙烷溶液。在搅拌1小时后，添加D₂O(5mL)。约0.5小时后，用DCM(二氯甲烷)提取混合物，并组合各个有机相，用卤水清洗，用Mg₂SO₄干燥。去除溶剂，得到一混合物(深褐色油质，497mg)，将粗品直接用于下一步骤：Synthesis of 2-bromo-4-D-pyridine: To a 100 mL flask was added 2,6-dibromopyridine (2.36 g, 10 mmol), dissolved in freshly distilled tetrahydrofuran (THF) at room temperature. A solution of i-PrMgBr (8 mL, 12.8 mmol) in n-ethane was then added dropwise. After stirring for 1 h,_D2O (5 mL) was added. After about 0.5 h, the mixture was extracted with DCM (dichloromethane) and the organic phases were combined, washed with brine and dried_overMg2SO4 . Removal of solvent gave a mixture (dark brown oil, 497 mg), the crude product was used directly in the next step:

络合物1的2-D-配体的合成：向一个15mL密封管添加1-甲基咪唑(16mg，0.2mmol)，2-(3-(1H-吡唑-1-基)苯氧基)-9H-咔唑(130mg，0.4mmol),2-溴-4-D-吡啶(346mg，2mmol)，K₂CO₃(111mg，0.8mmol)，甲苯(2mL)和CuI(15mg，0.08mmol)。用氮让混合物起泡10分钟，并在120℃下搅拌3天。在冷却后，添加水和乙酸乙酯(EA)，并对混合物进行过滤。采用乙酸乙酯提取水相，并组合各个有机相，用卤水清洗，用Na₂SO₄干燥。采用PE/EA＝10:1作为洗提液，通过硅胶层析来净化所获得的溶液，产生目标产品(浅褐色固体，160mg，99％良率)。¹H NMR(500MHz,DMSO-d⁶):δ8.55(d,J＝2.6Hz,1H)，8.33(d,J＝8.4Hz,1H)，8.28(d,J＝7.9Hz,1H)，8.13(t,J＝7.8Hz,1H)，7.84(s,1H)，7.82(s,1H)，7.73(d,J＝1.7Hz,1H)，7.64(d,J＝8.5Hz,1H)，7.60-7.56(m,2H)，7.54-7.47(m,3H)，7.39(t,J＝7.5Hz,1H)，7.14(dd,J＝8.4,2.2Hz,1H)，6.99(dd,J＝8.1,2.4Hz,1H)，6.56(s,1H)。MS(ESI):404.2[M+H⁺]，426.1[M+Na⁺]Synthesis of 2-D-ligand of complex 1: To a 15 mL sealed tube was added 1-methylimidazole (16 mg, 0.2 mmol), 2-(3-(1H-pyrazol-1-yl)phenoxy )-9H-carbazole (130mg, 0.4mmol), 2-bromo-4-D-pyridine (346mg, 2mmol), K₂ CO₃ (111mg, 0.8mmol), toluene (2mL) and CuI (15mg, 0.08mmol ). The mixture was bubbled with nitrogen for 10 minutes and stirred at 120°C for 3 days. After cooling, water and ethyl acetate (EA) were added, and the mixture was filtered. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, washed with brine and dried_overNa2SO4 . The obtained solution was purified by silica gel chromatography using PE/EA=10:1 as eluent to yield the target product (light brown solid, 160 mg, 99% yield).¹ H NMR (500MHz, DMSO-d⁶ ): δ8.55 (d, J=2.6Hz, 1H), 8.33 (d, J=8.4Hz, 1H), 8.28 (d, J=7.9Hz, 1H), 8.13(t, J=7.8Hz, 1H), 7.84(s, 1H), 7.82(s, 1H), 7.73(d, J=1.7Hz, 1H), 7.64(d, J=8.5Hz, 1H), 7.60-7.56(m,2H), 7.54-7.47(m,3H), 7.39(t,J=7.5Hz,1H), 7.14(dd,J=8.4,2.2Hz,1H), 6.99(dd,J= 8.1, 2.4Hz, 1H), 6.56(s, 1H). MS(ESI): 404.2[M+H⁺ ], 426.1[M+Na⁺ ]

络合物1的合成：向手套式操作箱中的一个15mL密封管添加2-D-配体(20mg，0.05mmol)、氯亚铂酸钾(23mg，0.055mmol)和乙酸(1mL)，并在用氮让混合物起泡15分钟后，将混合物加热到110℃，为时三天。在冷却至室温后，用水对所产生的溶液进行处理，并沉淀出少量固体。集取溶液，并采用DCM(二氯甲烷)作为洗提液，通过硅胶层析来净化溶液，产生目标产品(黄色固体，14mg，47％良率)。¹H NMR(300MHz,CDCl₃):δ8.26(d,J＝8.6Hz,1H)，8.13(d,J＝2.7Hz,1H)，8.02(d,J＝7.1Hz,1H)，7.98-7.88(m,2H)，7.84(s,1H)，7.79(d,J＝8.3Hz,1H)，7.44-7.29(m,3H)，7.21(d,J＝8.0Hz,1H)，7.16-7.06(m,3H)，6.67(s,1H)。室温下PMMA(聚甲基丙烯酸甲酯)中CIE(0.156,0.124)。Synthesis of complex 1: 2-D-ligand (20 mg, 0.05 mmol), potassium chloroplatinite (23 mg, 0.055 mmol) and acetic acid (1 mL) were added to a 15 mL sealed tube in a glove box, and After bubbling the mixture with nitrogen for 15 minutes, the mixture was heated to 110° C. for three days. After cooling to room temperature, the resulting solution was treated with water and a small amount of solid precipitated. The solution was collected and purified by silica gel chromatography using DCM (dichloromethane) as eluent to yield the target product (yellow solid, 14 mg, 47% yield).¹ H NMR (300MHz, CDCl₃ ): δ8.26(d, J=8.6Hz, 1H), 8.13(d, J=2.7Hz, 1H), 8.02(d, J=7.1Hz, 1H), 7.98- 7.88(m, 2H), 7.84(s, 1H), 7.79(d, J=8.3Hz, 1H), 7.44-7.29(m, 3H), 7.21(d, J=8.0Hz, 1H), 7.16-7.06 (m,3H), 6.67(s,1H). CIE (0.156,0.124) in PMMA (polymethyl methacrylate) at room temperature.

铂络合物1是按照以下方案制备：Platinum complex 1 was prepared according to the following scheme:

向手套箱中的一个15mL密封管添加配体(30mg，0.075mmol)、氯亚铂酸钾(31mg，0.075mmol)和乙酸(1mL)，并在让混合物起泡15分钟后，在110℃下对混合物进行加热，为时三天。在冷却至室温后，用水(10mL)对所产生的溶液进行处理，并沉淀出少量固体。集取溶液，并采用PE/DCM＝1:2作为洗提液，通过硅胶层析来净化溶液，产生目标产品(黄色固体，22mg，49％良率)。¹H NMR(500MHz,DMSO-d⁶):δ9.30(s,1H)，8.92(d,J＝2.7Hz,1H)，8.31(d,J＝8.6Hz,1H)，8.25(dd,J＝8.7,1.8Hz,1H)，8.20(d,J＝2.2Hz,1H)，8.18(d,J＝7.5Hz,1H)，8.11(d,J＝8.2Hz,1H)，7.90(d,J＝8.2Hz,1H)，7.53(d,J＝7.6Hz,1H)，7.50(t,J＝7.6Hz,1H)，7.43(t,J＝7.5Hz,1H)，7.25(d,J＝7.9Hz,1H)，7.24–7.22(m,1H)，7.00(d,J＝8.0Hz,1H)，6.93(t,J＝3.0Hz,1H)。Ligand (30 mg, 0.075 mmol), potassium chloroplatinite (31 mg, 0.075 mmol) and acetic acid (1 mL) were added to a 15 mL sealed tube in the glove box, and after allowing the mixture to bubble for 15 minutes, the The mixture was heated for three days. After cooling to room temperature, the resulting solution was treated with water (10 mL) and a small amount of solid precipitated. The solution was collected and purified by silica gel chromatography using PE/DCM=1:2 as the eluent to yield the target product (yellow solid, 22 mg, 49% yield).¹ H NMR (500MHz, DMSO-d⁶ ): δ9.30(s, 1H), 8.92(d, J=2.7Hz, 1H), 8.31(d, J=8.6Hz, 1H), 8.25(dd, J =8.7,1.8Hz,1H), 8.20(d,J=2.2Hz,1H), 8.18(d,J=7.5Hz,1H), 8.11(d,J=8.2Hz,1H), 7.90(d,J =8.2Hz, 1H), 7.53(d, J=7.6Hz, 1H), 7.50(t, J=7.6Hz, 1H), 7.43(t, J=7.5Hz, 1H), 7.25(d, J=7.9 Hz, 1H), 7.24–7.22 (m, 1H), 7.00 (d, J=8.0Hz, 1H), 6.93 (t, J=3.0Hz, 1H).

铂络合物3是按照以下方案制备：Platinum complex 3 was prepared according to the following scheme:

2-(苄氧基溴)-(4-D-吡啶-2-基)-9H-咔唑的合成：向一个15mL密封管添加2-(苄氧基)-9-(4-溴吡啶-2-基)-9H-咔唑(107mg，0.25mmol)。然后在室温下逐滴添加iPrMgBr(1.5mL，1M)的四氢呋喃(THF)溶液。在搅拌1小时后，添加D₂O(0.6mL)。30分钟后，用Na₂SO₄对混合物进行干燥。采用PE/EA＝15:1作为洗提液，通过硅胶层析来净化所产生的溶液，产生再循环的反应物(白色固体，13mg)和目标产品(浅褐色固体，75mg，85％良率)。¹H NMR(300MHz,DMSO-d⁶):δ8.77(d,J＝4.9Hz,1H)，8.16(d,J＝8.4Hz,2H)，7.78(d,J＝8.9Hz,2H)，7.52(d,J＝6.2Hz,3H)，7.40-7.36(m,5H)，7.32(t,J＝7.4Hz,1H)，7.07(dd,J＝8.1,1.2Hz,1H)，5.22(s,2H).MS(ESI):351.2[M+H⁺]，373.1[M+Na⁺]。Synthesis of 2-(benzyloxybromo)-(4-D-pyridin-2-yl)-9H-carbazole: To a 15 mL sealed tube was added 2-(benzyloxy)-9-(4-bromopyridine- 2-yl)-9H-carbazole (107 mg, 0.25 mmol). A solution of iPrMgBr (1.5 mL, 1M) in tetrahydrofuran (THF) was then added dropwise at room temperature. After stirring for 1 h,_D2O (0.6 mL) was added. After 30 minutes, the mixture was dried_overNa2SO4 . Purification of the resulting solution by silica gel chromatography using PE/EA=15:1 as eluent yielded recycled reactant (white solid, 13 mg) and target product (light brown solid, 75 mg, 85% yield ).¹ H NMR (300MHz, DMSO-d⁶ ): δ8.77 (d, J=4.9Hz, 1H), 8.16 (d, J=8.4Hz, 2H), 7.78 (d, J=8.9Hz, 2H), 7.52(d, J=6.2Hz, 3H), 7.40-7.36(m, 5H), 7.32(t, J=7.4Hz, 1H), 7.07(dd, J=8.1, 1.2Hz, 1H), 5.22(s ,2H). MS (ESI): 351.2 [M+H⁺ ], 373.1 [M+Na⁺ ].

9-(4-D-吡啶-2-基)-9H-咔唑-2-丙醇的合成：向一个高压釜添加2-(苄氧基)-9-(4-D-吡啶-2-基)-9H-咔唑(331mg，0.9mmol)、Pd/C(38mg)和EA(25mL)。将混合物排空，再用氮重新填充，操作三次，并在0.8MPa和65℃下搅拌24小时。在冷却下来后，对混合物进行过滤并用Na₂SO₄对过滤液进行干燥。采用PE/EA＝10:1,2:1作为洗提液，通过硅胶层析来净化所获得的溶液，产生再循环的反应物(浅褐色固体，6mg)和目标产品(白色固体，231mg，98％良率)。¹H NMR(300MHz,DMSO-d⁶):δ9.60(s,1H)，8.76(d,J＝4.9Hz,1H)，8.13-8.06(m,1H)，8.03(d,J＝8.4Hz,1H)，7.78(s,1H)，7.73(d,J＝8.1Hz,1H)，7.51(d,J＝4.7Hz,1H)，7.41-7.32(t,J＝7.7Hz,1H)，7.29(t,J＝7.7Hz,1H)，7.21(d,J＝2.1Hz,1H)，6.82(dd,J＝8.4,2.1Hz,1H)。MS(ESI):262.1[M+H⁺].Synthesis of 9-(4-D-pyridin-2-yl)-9H-carbazole-2-propanol: Add 2-(benzyloxy)-9-(4-D-pyridine-2- base)-9H-carbazole (331 mg, 0.9 mmol), Pd/C (38 mg) and EA (25 mL). The mixture was evacuated and refilled three times with nitrogen and stirred at 0.8 MPa and 65° C. for 24 hours. After cooling down, the mixture was filtered and the filtrate was dried_overNa2SO4 . Purification of the obtained solution by silica gel chromatography using PE/EA=10:1, 2:1 as eluent yielded recycled reactant (light brown solid, 6 mg) and target product (white solid, 231 mg, 98% yield).¹ H NMR (300MHz, DMSO-d⁶ ): δ9.60(s, 1H), 8.76(d, J=4.9Hz, 1H), 8.13-8.06(m, 1H), 8.03(d, J=8.4Hz ,1H), 7.78(s,1H), 7.73(d,J=8.1Hz,1H), 7.51(d,J=4.7Hz,1H), 7.41-7.32(t,J=7.7Hz,1H), 7.29 (t, J=7.7Hz, 1H), 7.21 (d, J=2.1Hz, 1H), 6.82 (dd, J=8.4, 2.1Hz, 1H). MS(ESI):262.1[M+H⁺ ].

络合物1的4-D-配体的合成：向一个15mL密封管添加3-甲基咪唑(16mg，0.2mmol)，4-(3-(1H-吡唑-1-基)苯氧基)-9H-咔唑(130mg，0.4mmol),2-溴-4-D-吡啶(235mg，0.9mmol)，K₂CO₃(880mg，2.7mmol)，甲苯(2mL)和CuI(0.18mmol，10m)。用氮让混合物起泡10分钟，并在120℃下搅拌3天。在冷却后，添加水和乙酸乙酯(EA)，并对混合物进行过滤。采用乙酸乙酯提取水相，并组合各个有机相，用卤水清洗，用Na₂SO₄干燥。采用PE/EA＝10:1作为洗提液，通过硅胶层析来净化所获得的溶液，产生目标产品(浅褐色固体，75mg，99％良率)。¹H NMR(500MHz,DMSO-d⁶):δ8.72(d,J＝4.9Hz,1H)，8.54(d,J＝8.4Hz,1H)，8.28(d,J＝7.9Hz,1H)，7.13(t,J＝7.8Hz,1H)，7.84(s,1H)，7.82(s,1H)，7.73(d,J＝1.7Hz,1H)，7.64(d,J＝8.5Hz,1H)，7.60-7.56(m,2H)，7.54-7.47(m,3H)，7.39(t,J＝7.5Hz,1H)，7.14(dd,J＝8.4,2.2Hz,1H)，7.59(dd,J＝8.1,2.4Hz,1H)，6.55(s,1H)。MS(ESI):404.2[M+H⁺]，426.1[M+Na⁺]。Synthesis of 4-D-ligand of complex 1: To a 15 mL sealed tube was added 3-methylimidazole (16 mg, 0.2 mmol), 4-(3-(1H-pyrazol-1-yl)phenoxy )-9H-carbazole (130mg, 0.4mmol), 2-bromo-4-D-pyridine (235mg, 0.9mmol), K₂ CO₃ (880mg, 2.7mmol), toluene (2mL) and CuI (0.18mmol, 10m). The mixture was bubbled with nitrogen for 10 minutes and stirred at 120°C for 3 days. After cooling, water and ethyl acetate (EA) were added, and the mixture was filtered. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, washed with brine and dried_overNa2SO4 . The obtained solution was purified by silica gel chromatography using PE/EA=10:1 as eluent to yield the target product (light brown solid, 75 mg, 99% yield).¹ H NMR (500MHz, DMSO-d⁶ ): δ8.72 (d, J=4.9Hz, 1H), 8.54 (d, J=8.4Hz, 1H), 8.28 (d, J=7.9Hz, 1H), 7.13(t, J=7.8Hz, 1H), 7.84(s, 1H), 7.82(s, 1H), 7.73(d, J=1.7Hz, 1H), 7.64(d, J=8.5Hz, 1H), 7.60-7.56(m,2H), 7.54-7.47(m,3H), 7.39(t,J=7.5Hz,1H), 7.14(dd,J=8.4,2.2Hz,1H), 7.59(dd,J= 8.1,2.4Hz,1H), 6.55(s,1H). MS (ESI): 404.2 [M+H⁺ ], 426.1 [M+Na⁺ ].

络合物3的合成：向一个15mL密封管添加4-D-配体(20mg，0.05mmol)、氯亚铂酸钾(23mg，0.055mmol)和乙酸(1mL)，并在用氮让混合物起泡15分钟后，将混合物加热到110℃，为时三天。在冷却至室温后，用水对所产生的溶液进行处理，并沉淀出少量固体。集取溶液，并采用DCM(二氯甲烷)作为洗提液，通过硅胶层析来净化溶液，产生目标产品(黄色固体，9mg，47％良率)。¹H NMR(500MHz,DMSO-d⁶):δ9.31(d,J＝5.9Hz,1H)，8.94(d,J＝2.7Hz,1H)，8.32(s,1H)，8.21(d,J＝2.2Hz,1H)，8.19(d,J＝6.8Hz,1H)，8.12(d,J＝8.5Hz,1H)，7.91(d,J＝8.3Hz,1H)，7.55(d,J＝7.7Hz,1H)，7.51(t,J＝7.7Hz,1H)，7.47-7.42(m,2H)，7.28-7.23(m,2H)，7.01(d,J＝8.0Hz,1H)，6.94(t,J＝2.5Hz,1H)。室温下PMMA(聚甲基丙烯酸甲酯)中CIE(0.155,0.117)。Synthesis of complex 3: 4-D-ligand (20 mg, 0.05 mmol), potassium chloroplatinite (23 mg, 0.055 mmol) and acetic acid (1 mL) were added to a 15 mL sealed tube, and the mixture was stirred under nitrogen. After soaking for 15 minutes, the mixture was heated to 110°C for three days. After cooling to room temperature, the resulting solution was treated with water and a small amount of solid precipitated. The solution was collected and purified by silica gel chromatography using DCM (dichloromethane) as eluent to yield the target product (yellow solid, 9 mg, 47% yield).¹ H NMR (500MHz, DMSO-d⁶ ): δ9.31(d, J=5.9Hz, 1H), 8.94(d, J=2.7Hz, 1H), 8.32(s, 1H), 8.21(d, J =2.2Hz, 1H), 8.19(d, J=6.8Hz, 1H), 8.12(d, J=8.5Hz, 1H), 7.91(d, J=8.3Hz, 1H), 7.55(d, J=7.7 Hz, 1H), 7.51(t, J=7.7Hz, 1H), 7.47-7.42(m, 2H), 7.28-7.23(m, 2H), 7.01(d, J=8.0Hz, 1H), 6.94(t , J=2.5Hz, 1H). CIE (0.155,0.117) in PMMA (polymethyl methacrylate) at room temperature.

铂络合物4是按照以下方案制备：Platinum complex 4 was prepared according to the following scheme:

络合物4的5-D-配体的合成：向一个48mL密封管添加2-溴-9-(3-D-吡啶-2-基)-9H-咔唑(196mg，0.6mmol)、N-(3-羟苯基)吡唑(80mg，0.5mmol)、N,N-二甲基甘氨酸(15mg，0.15mmol)，Cs₂CO₃ 489mg，1.5mmol)，CuI(14mg，0.075mmol)和1,4-二氧六环(5mL)。用氮让混合物起泡10分钟，并在120℃下搅拌3天。在冷却后，去除溶剂。用水和乙酸乙酯(EA)对混合物进行处理，并对其进行过滤。采用乙酸乙酯提取水相，并组合各个有机相，用卤水清洗，用Na₂SO₄干燥。采用PE/EA＝10:1作为洗提液，通过硅胶层析来净化所获得的溶液，产生目标产品(浅褐色固体，144mg，71％良率)。¹H NMR(500MHz,DMSO-d⁶):δ8.72(dd,J＝4.8,2.0Hz,1H),8.54(d,J＝2.6Hz,1H)，8.32(d,J＝8.4Hz,1H)，8.27(d,J＝7.7Hz,1H)，8.12(dd,J＝7.4,1.9Hz,1H)，7.83(d,J＝8.3Hz,1H)，7.73(d,J＝1.7Hz,1H)，7.63(dd,J＝8.1,2.1Hz,1H)，7.59(d,J＝2.2Hz,1H)，7.57(t,J＝2.2Hz,1H)，7.53-7.47(m,3H)，7.39(t,J＝7.4Hz,1H)，7.13(dd,J＝8.5,2.2Hz,1H)，6.99(dd,J＝7.9,2.4Hz,1H)，6.55(t,J＝2.2Hz,1H)。Synthesis of 5-D-ligand of complex 4: To a 48 mL sealed tube was added 2-bromo-9-(3-D-pyridin-2-yl)-9H-carbazole (196 mg, 0.6 mmol), N -(3-hydroxyphenyl)pyrazole (80mg, 0.5mmol), N,N-dimethylglycine (15mg, 0.15mmol), Cs₂ CO₃ 489mg, 1.5mmol), CuI (14mg, 0.075mmol) and 1,4-Dioxane (5 mL). The mixture was bubbled with nitrogen for 10 minutes and stirred at 120°C for 3 days. After cooling, the solvent was removed. The mixture was treated with water and ethyl acetate (EA) and filtered. The aqueous phase was extracted with ethyl acetate and the organic phases were combined, washed with brine and dried_overNa2SO4 . The obtained solution was purified by silica gel chromatography using PE/EA=10:1 as eluent to yield the target product (light brown solid, 144 mg, 71% yield).¹ H NMR (500MHz, DMSO-d⁶ ): δ8.72(dd, J=4.8, 2.0Hz, 1H), 8.54(d, J=2.6Hz, 1H), 8.32(d, J=8.4Hz, 1H ), 8.27(d, J=7.7Hz, 1H), 8.12(dd, J=7.4, 1.9Hz, 1H), 7.83(d, J=8.3Hz, 1H), 7.73(d, J=1.7Hz, 1H ), 7.63(dd, J=8.1,2.1Hz,1H), 7.59(d,J=2.2Hz,1H), 7.57(t,J=2.2Hz,1H), 7.53-7.47(m,3H), 7.39 (t,J=7.4Hz,1H), 7.13(dd,J=8.5,2.2Hz,1H), 6.99(dd,J=7.9,2.4Hz,1H), 6.55(t,J=2.2Hz,1H) .

络合物4的合成：向一个15mL密封管添加5-D-配体(40mg，0.1mmol)、氯亚铂酸钾(46mg，0.11mmol)和乙酸(1mL)，并在用N₂让混合物起泡10分钟后，在110℃下对混合物进行加热，为时三天。在冷却至室温后，用水对所产生的溶液进行处理，并沉淀出少量固体。集取溶液，并采用PE/DCM＝1:1作为洗提液，通过硅胶层析来净化溶液，产生目标产品(黄色固体，8mg，13％良率)。¹H NMR(300MHz,DMSO-d⁶):δ9.31(d,J＝5.3Hz,1H)，8.94(d,J＝2.7Hz,1H)，8.27(dd,J＝6.9,1.2Hz,1H)，8.24-8.16(m,2H)，8.12(d,J＝8.1Hz,1H)，7.91(d,J＝8.3Hz,1H)，7.54(t,J＝7.3Hz,2H)，7.50-7.40(m,2H)，7.31-7.19(m,2H)，7.01(d,J＝8.0Hz,1H)，6.94(t,J＝2.4Hz,1H)。室温下PMMA(聚甲基丙烯酸甲酯)中CIE(0.146,0.109)。Synthesis of complex 4: Add 5-D-ligand (40 mg, 0.1 mmol), potassium chloroplatinite (46 mg, 0.11 mmol) and acetic acid (₁ mL) to a 15 mL sealed tube, and let the mixture After 10 minutes of foaming, the mixture was heated at 110°C for three days. After cooling to room temperature, the resulting solution was treated with water and a small amount of solid precipitated. The solution was collected and purified by silica gel chromatography using PE/DCM=1:1 as the eluent to yield the target product (yellow solid, 8 mg, 13% yield).¹ H NMR (300MHz, DMSO-d⁶ ): δ9.31 (d, J=5.3Hz, 1H), 8.94 (d, J=2.7Hz, 1H), 8.27 (dd, J=6.9, 1.2Hz, 1H ), 8.24-8.16(m, 2H), 8.12(d, J=8.1Hz, 1H), 7.91(d, J=8.3Hz, 1H), 7.54(t, J=7.3Hz, 2H), 7.50-7.40 (m, 2H), 7.31-7.19 (m, 2H), 7.01 (d, J=8.0Hz, 1H), 6.94 (t, J=2.4Hz, 1H). CIE (0.146,0.109) in PMMA (polymethyl methacrylate) at room temperature.

铂络合物3是按照以下方案制备：Platinum complex 3 was prepared according to the following scheme:

配体络合物7的合成：向一个15mL密封管添加4-CH₃-配体(42mg，0.1mmol)、CH₃CH₂ONa(14mg,0.2mmol)和CH₃CH₂OD(1mL)。用氮让混合物起泡10分钟后，并让混合物回流3天。在冷却至室温后，用乙酸乙酯来提取溶液，并组合各个有机相，用卤水清洗，用Na₂SO₄干燥。采用PE/EA＝5:1作为洗提液，通过硅胶层析来净化所产生的溶液，产生目标产品(白色固体，42mg的4-³d-配体，100％良率)。¹H NMR(300MHz,CDCl₃):δ8.55(d,J＝4.8Hz,1H)、8.08(s,1H)、8.05(s,1H)、7.77(d,J＝8.5Hz,1H)、7.68(s,1H)、7.54(s,1H)、7.49-7.31(m,7H)、7.14(s,1H)、7.05(d,J＝8.4Hz,1H)、6.95(d,J＝7.8Hz,1H)、6.43(s,1H)。Synthesis of Ligand Complex 7: To a 15 mL sealed tube was added 4-CH₃ -ligand (42 mg, 0.1 mmol), CH₃ CH₂ ONa (14 mg, 0.2 mmol) and CH₃ CH₂ OD (1 mL). After bubbling the mixture with nitrogen for 10 minutes, the mixture was refluxed for 3 days. After cooling to room temperature, the solution was extracted with ethyl acetate and the organic phases were combined, washed with brine and dried_overNa2SO4 . The resulting solution was purified by silica gel chromatography using PE/EA=5:1 as eluent to yield the target product (white solid, 42 mg of 4-3d^- ligand, 100% yield).¹ H NMR (300MHz, CDCl₃ ): δ8.55(d, J=4.8Hz, 1H), 8.08(s, 1H), 8.05(s, 1H), 7.77(d, J=8.5Hz, 1H), 7.68(s,1H), 7.54(s,1H), 7.49-7.31(m,7H), 7.14(s,1H), 7.05(d,J=8.4Hz,1H), 6.95(d,J=7.8Hz ,1H), 6.43(s,1H).

络合物7的合成：向一个15mL密封管添加4-CD₃-配体(42mg，0.1mmol)、氯亚铂酸钾(46mg，0.11mmol)和乙酸(1mL)。用氮让混合物起泡10分钟，并将混合物加热至110℃，为时三天。在冷却至室温后，用水对所产生的溶液进行处理，并沉淀出少量固体。集取溶液，并采用PE/DCM＝1:2作为洗提液，通过硅胶层析来净化溶液，产生目标产品(黄色固体，23mg，38％良率)。¹H NMR(300MHz,CDCl₃):δ9.10(d,J＝5.7Hz,1H)，8.08-7.99(m,2H)，7.92(d,J＝8.0Hz,1H)，7.82(s,1H)，7.78(d,J＝8.2Hz,1H)，7.35(m,4H)，7.20(m,1H)，7.11(m,2H)，6.94(d,J＝6.2Hz,1H)，6.66(d,J＝1.8Hz,1H)。Synthesis of complex 7: To a 15 mL sealed tube was added 4-_CD3 -ligand (42 mg, 0.1 mmol), potassium chloroplatinite (46 mg, 0.11 mmol) and acetic acid (1 mL). The mixture was bubbled with nitrogen for 10 minutes, and the mixture was heated to 110° C. for three days. After cooling to room temperature, the resulting solution was treated with water and a small amount of solid precipitated. The solution was collected and purified by silica gel chromatography using PE/DCM=1:2 as the eluent to yield the target product (yellow solid, 23 mg, 38% yield).¹ H NMR (300MHz, CDCl₃ ): δ9.10(d, J=5.7Hz, 1H), 8.08-7.99(m, 2H), 7.92(d, J=8.0Hz, 1H), 7.82(s, 1H ), 7.78(d, J=8.2Hz,1H), 7.35(m,4H), 7.20(m,1H), 7.11(m,2H), 6.94(d,J=6.2Hz,1H), 6.66(d , J=1.8Hz, 1H).

发射光谱显示在向配基添加氘原子时，三线态能隙几乎是相同的。The emission spectrum shows that the triplet energy gap is almost the same when deuterium atoms are added to the ligand.

发射体色纯度的代表性数据是从其采用5％PMMA(聚甲基丙烯酸甲酯)三氯甲烷溶液制备的薄膜发射光谱获得。PMMA(聚甲基丙烯酸甲酯)中的CIE指数坐标是非氘化络合物(0.163,0.131)，络合物1(0.156,0.124)，络合物2(0.160,0.119)，络合物3(0.155,0.117)和络合物4(0.146,0.109)。可通过氘化来提高色纯度。在图7所示氘化甲基取代的络合物7的情况下，与其CIE坐标为(0.147,0.100)的非氘化络合物7相比，室温下DCM(二氯甲烷)溶液中的发射光谱在深蓝色区域显示出更佳的CIE坐标(0.145,0.093)。Representative data for the color purity of the emitters were obtained from the emission spectra of films prepared using 5% PMMA (polymethyl methacrylate) in chloroform. The CIE index coordinates in PMMA (polymethyl methacrylate) are non-deuterated complex (0.163, 0.131), complex 1 (0.156, 0.124), complex 2 (0.160, 0.119), complex 3 (0.155,0.117) and complex 4 (0.146,0.109). Color purity can be improved by deuteration. In the case of the deuterated methyl-substituted complex 7 shown in Figure 7, compared with its non-deuterated complex 7 with CIE coordinates of (0.147, 0.100), the DCM (dichloromethane) solution at room temperature The emission spectrum shows better CIE coordinates (0.145, 0.093) in the dark blue region.

本领域的普通技术人员基于本说明书，会明白各方面的其他修改和替代性具体实施方式。因此，本说明书仅可解释为是解说性的。应理解，应将本文所显示和说明的形式作为具体实施方式的示例。本文所解说和说明者可用其他元件和材料来替代，部件和程序可以反向，并可以独立应用特定的特征，对于所有这些，本领域的普通技术人员在从本说明书中获益后均会明白。可对本文说明的元件作更改，而不脱离下面权利要求书中所述的精神和范围。Other modifications and alternative specific implementations of various aspects will be apparent to those skilled in the art based on this description. Accordingly, the specification is to be interpreted as illustrative only. It should be understood that the forms shown and described herein are to be considered as examples of specific embodiments. What has been illustrated and described herein may be substituted with other elements and materials, parts and procedures may be reversed, and specific features may be applied independently, all of which will be apparent to those of ordinary skill in the art having the benefit of this specification . Changes may be made in the elements described herein without departing from the spirit and scope described in the following claims.

Claims (10)

Translated fromChinese

1.一种铂化合物，其特征在于，具有以下分子式：1. A platinum compound, characterized in that, has the following molecular formula:其中R^a代表单、双、三或四基取代，R^a是独立的氘，R^a独立构成CDH₂，CD₂H，CD₃，CD R¹R²，CD₂R¹，或其他含氘的烷基芳、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单取代氨基、二烃基氨基、单氨基、二芳基胺、烷氧基、芳氧基、卤代基、芳烷基、酯、烷氧羰基、酰胺基、烷氧基羰基氨基，烷氧基碳酰基氨基、芳氧基碳酰基氨基、芳烷基、氨磺酰、氨基甲酰基、烷硫基，脲基、磷酰胺、甲硅烷基、聚合物；或其任何结合物或化合物；Wherein R^a represents mono-, di-, tri- or tetra-substitution, R^a is independent deuterium, and R^a independently constitutes CDH₂ , CD₂ H, CD₃ , CD R¹ R² , CD₂ R¹ , or other deuterium-containing Alkylaryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monosubstituted amino, dihydrocarbylamino, monoamino, diarylamine, alkoxy radical, aryloxy, halo, aralkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aralkyl, sulfonamide , carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any combination or compound thereof;R^b、R^c、R^d和R^e中的每一种都是要么独立存在的或不存在的，如果是存在的，那么R^b、R^c、R^d和R^e中的每一种分别代表单或双基取代，R^b,R^d和R^e也可以是三基取代，R^b可以是四基取代，并且其中R^b、R^c、R^d和R^e中的每一种是独立的氘、卤素、羟基、巯基、硝基、氰基、腈、异腈、亚磺酰基、巯基、磺基、羧基、肼基；取代或未取代的：芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤代烷基、芳烷基、酯、烷氧基羰基、酰基氨基、烷氧基羰基氨基、芳基含氧羰基氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物，R^a和R^b可选择性地连接形成熔合环，R^d和R^e可选择性地连接形成熔合环；Each of R^b , R^c , R^d and^Re is either independently present or absent, and if present, each of R^b , R^c , R^d and^Re respectively Represents single or double substitution, R^b , R^d and^Re may also be tri-substitution, R^b may be tetra-substitution, and each of R^b , R^c , R^d and^Re is independently Deuterium, halogen, hydroxyl, mercapto, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl , heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl , aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, sulfonamide, carbamoyl, alkylthio, ureido, phosphoramide, Silyl, polymerization; or any combination or compound thereof, R^a and R^b can be optionally connected to form a fusion ring, R^d and R^e can be optionally connected to form a fusion ring;R¹和R²中的每一种都是独立的氢、氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、氧芳基、卤烷基、芳烷基,、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、硫烷基、脲基、磷酰胺、甲硅烷基、聚合物；或其任何结合物或化合物。Each^of R and R is independently^hydrogen , deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternative or irreplaceable: aryl, cycloalkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkyl Amino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, Aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, sulfanyl, ureido, phosphoramide, silyl, polymer; or any combination or compound thereof.2.根据权利要求1所述的铂化合物，其特征在于：所述化合物还具有分子式二、分子式三、分子式四、分子式五、分子式六或分子式七的结构；2. The platinum compound according to claim 1, characterized in that: the compound also has the structure of molecular formula 2, molecular formula 3, molecular formula 4, molecular formula 5, molecular formula 6 or molecular formula 7;R^b、R^c、R^d和R^e中的每一种都是要么独立存在的或不存在的，如果是存在的，那么R^b、R^c、R^d和R^e中的每一种分别代表单或双基取代，R^b,R^d和R^e也可以是三基取代，R^b可以是四基取代，并且其中R^b、R^c、R^d和R^e中的每一种是独立的氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；替代或不替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物，R^a和R^b可选择性地连接形成熔合环，R^d和R^e可选择性地连接形成熔合环。Each of R^b , R^c , R^d and^Re is either independently present or absent, and if present, each of R^b , R^c , R^d and^Re respectively Represents single or double substitution, R^b , R^d and^Re may also be tri-substitution, R^b may be tetra-substitution, and each of R^b , R^c , R^d and^Re is independently deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternatively or not: aryl, cyclic Alkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino , alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, sulfonamide, carbamoyl, alkane Thio group, ureido group, phosphoramidite, silyl group, polymerization; or any combination or compound thereof, R^a and R^b can be optionally linked to form a fusion ring, R^d and R^e can be optionally linked to form a fusion ring .R¹和R²中的每一种都是独立的氢、氘、卤素、羟氢氧基、硫醇、硝基、氰基、腈、异腈、亚硫酰基、氢硫基、磺基、羧基、肼基；可替代或不可替代的：芳基、环烷基烷基、环烯基环烯基、杂环基、杂芳基、烷基、烯基、炔基、氨基、单烷基氨基、二烷基氨基、单芳基氨基、二芳基氨基、烷氧基、芳氧基、卤烷基、烷基、酯、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧羰氨基、硫酰氨基、氨磺酰、氨基甲酰、烷硫基、脲基、磷酰胺、甲硅烷基、聚合；或其任何结合物或化合物。Each^of R and R is independently^hydrogen , deuterium, halogen, hydroxyhydroxyl, mercaptan, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; alternative or irreplaceable: aryl, cycloalkylalkyl, cycloalkenylcycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkyl Amino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, alkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxy Carbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any combination or compound thereof.3.根据权利要求1所述的铂化合物，其特征在于：其中R^d和R^e连接形成熔合环并可以选自以下结构：3. platinum compound according to claim 1, is characterized in that: wherein^R and^Re are joined to form a fused ring and can be selected from the following structures:4.根据权利要求1-3中任意一项所述的铂化合物，其特征在于：所述铂化合物具有中性电荷。4. The platinum compound according to any one of claims 1-3, characterized in that: the platinum compound has a neutral charge.5.根据权利要求1-3中任意一项所述铂化合物，其特征在于：所述铂化合物是从由络合物1至络合物312组成的群组中选择：5. The platinum compound according to any one of claims 1-3, characterized in that: the platinum compound is selected from the group consisting of complexes 1 to 312:6.一种发射体，其特征在于：所述发射体是一延迟荧光发射体和/或磷光发射体，包括权利要求1所述的铂化合物。6. An emitter, characterized in that: the emitter is a delayed fluorescence emitter and/or phosphorescence emitter, comprising the platinum compound as claimed in claim 1.7.根据权利要求6所述的发射体，其特征在于：所述化合物经选择为在器件环境中具有100％内部量子效率。7. The emitter of claim 6, wherein the compound is selected to have 100% internal quantum efficiency in the device environment.8.根据权利要求8所述的发射体，其特征在于：所述发射体是有机发光二极管。8. The emitter according to claim 8, characterized in that the emitter is an organic light emitting diode.9.根据权利要求1所述的铂化合物，其特征在于：所述铂化合物中聚合包含聚烷基、聚酯或聚醚。9. The platinum compound according to claim 1, characterized in that: the polymerization in the platinum compound comprises polyalkylene, polyester or polyether.10.根据权利要求9所述的铂化合物，其特征在于：聚合包含-(CH₂O)_n-CH₃、-(CH₂CH₂O)_n-CH₃、-[CH₂CH(CH₃)]_n-CH₃、-[CH₂CH(COOCH₃)]_n-CH₃、-[CH₂CH(COOCH₂CH₃)]_n-CH₃或-[CH₂CH(COO^tBu)]_n-CH₃，其中n是一整数。10. The platinum compound according to claim 9, characterized in that the polymerization comprises -(CH₂ O)_n -CH₃ , -(CH₂ CH₂ O)_n -CH₃ , -[CH₂ CH(CH₃ )]_n -CH₃ , -[CH₂ CH(COOCH₃ )]_n -CH₃ , -[CH₂ CH(COOCH₂ CH₃ )]_n -CH₃ or -[CH₂ CH(COO^t Bu)]_{n -} CH₃ , where n is an integer.