WO2023024445A1 - 螺环化合物、制剂、有机电致发光二极管及显示装置 - Google Patents

螺环化合物、制剂、有机电致发光二极管及显示装置 Download PDF

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WO2023024445A1
WO2023024445A1 PCT/CN2022/075574 CN2022075574W WO2023024445A1 WO 2023024445 A1 WO2023024445 A1 WO 2023024445A1 CN 2022075574 W CN2022075574 W CN 2022075574W WO 2023024445 A1 WO2023024445 A1 WO 2023024445A1
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substituted
unsubstituted
group
heteroaryl
spiro
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赵晓宇
申屠晓波
吴空物
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浙江华显光电科技有限公司
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Priority to JP2023547277A priority patent/JP2024507467A/ja
Priority to EP22859804.1A priority patent/EP4276103A1/en
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    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
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    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to a spiro compound, in particular to a spiro compound and an organic electroluminescent diode comprising the compound, belonging to the field of organic photoelectricity.
  • organic light-emitting diode As a new type of display technology, organic light-emitting diode (OLED) has self-illumination, wide viewing angle, low energy consumption, high efficiency, thin, rich colors, fast response, wide applicable temperature range, low driving voltage, and flexible
  • OLED organic light-emitting diode
  • OLED luminescence is divided into two ways: fluorescence luminescence and phosphorescence. According to theoretical speculation, the singlet excited state and triplet excited state formed by charge recombination The ratio is 1:3. Small molecule fluorescent materials can utilize 25% of the energy, and the remaining 75% of the energy is lost due to the non-luminescent mechanism of the triplet excited state, so it is generally believed that the internal quantum efficiency limit of fluorescent materials is 25%.
  • MR-TADF multiple resonance-induced thermally activated delayed fluorescence
  • MR-TADF molecules Because the skeleton of MR-TADF molecules is a planar structure, molecular stacking is easy to occur under solid-state conditions, and the strong interaction between light-emitting molecules can easily cause aggregation-induced fluorescence quenching, thereby reducing the luminous efficiency of MR-TADF OLED devices.
  • the organic electroluminescent diode comprising the organic compound has better efficiency, higher lifetime and reduced driving voltage.
  • the object of the present invention is to provide a spiro compound and an organic electroluminescent diode comprising the spiro compound, which has better efficiency and longer life and reduced drive voltage.
  • the present invention provides spiro compound, its structure is shown as formula (I):
  • a 1 and A 2 are each independently selected from the group consisting of:
  • B1, B2, B3, B4, C1, C2 and D1 are each independently selected from a C6-C60 aryl group or a C1-C60 heteroaryl group;
  • B1, B2, B3, B4, C1, C2 and D1 can undergo single or multiple substitutions according to the principle of valence bonds
  • X is selected from C, O, N, S or Se
  • R 1 , R and R 2 are each independently selected from hydrogen, deuterium, halogen, C1 ⁇ C18 alkyl, C1 ⁇ C18 alkoxy, C1 ⁇ C18 alkylsilyl, C1 ⁇ C18 alkoxysilyl, C6 ⁇ C40 substituted or unsubstituted aryl group, C1 ⁇ C40 heteroaryl group, C1 ⁇ C60 substituted or unsubstituted heterospiro ring, C1 ⁇ C60 substituted or unsubstituted spiro ring, substituted or unsubstituted aryl ether group, Substituted or unsubstituted heteroaryl ether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroaryl group Silyl, substituted or unsubstituted aryloxysilyl, substituted
  • the undeuterated groups in the above structures may be partially or fully deuterated.
  • said B1, B2, B3 and B4 are each independently selected from the group consisting of:
  • R is independently selected from hydrogen, deuterium, halogen, C1-C18 alkyl, C1-C18 alkoxy, C1-C18 alkylsilyl, C1-C18 alkoxysilyl, C6-C40 substituted or unsubstituted Aryl, C1 ⁇ C40 heteroaryl, C1 ⁇ C60 substituted or unsubstituted heterospiro ring, C1 ⁇ C60 substituted or unsubstituted spiro ring, substituted or unsubstituted aryl ether group, substituted or unsubstituted Heteroaryl ether, substituted or unsubstituted arylamine, substituted or unsubstituted heteroarylamine, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or Unsubstituted aryloxysilyl, substituted or unsubstituted aryl acyl, substituted or
  • the undeuterated groups in the above structures may be partially or fully deuterated.
  • said C1 and C2 are each independently selected from the following structures:
  • R is selected from hydrogen, deuterium, halogen, C1 ⁇ C18 alkyl, C1 ⁇ C18 alkoxy, C1 ⁇ C18 alkylsilyl, C1 ⁇ C18 alkoxysilyl, C6 ⁇ C40 substituted or unsubstituted aromatic C1-C40 heteroaryl group, C1-C60 substituted or unsubstituted heterospiro ring, C1-C60 substituted or unsubstituted spiro ring, substituted or unsubstituted aryl ether group, substituted or unsubstituted heteroaryl Ether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroarylsilyl group, substituted or unsubstituted Aryloxysilyl, substituted or unsubstituted aryl acyl,
  • X is selected from C, O, N, S or Se
  • Groups that have not been deuterated in the above structure can be partially or fully deuterated;
  • the dotted line indicates the formation of a chemical bond with the six-membered ring in the above structure.
  • said D1 is selected from the following structures:
  • R is selected from hydrogen, deuterium, halogen, C1 ⁇ C18 alkyl, C1 ⁇ C18 alkoxy, C1 ⁇ C18 alkylsilyl, C1 ⁇ C18 alkoxysilyl, C6 ⁇ C40 substituted or unsubstituted aromatic C1-C40 heteroaryl group, C1-C60 substituted or unsubstituted heterospiro ring, C1-C60 substituted or unsubstituted spiro ring, substituted or unsubstituted aryl ether group, substituted or unsubstituted heteroaryl Ether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroarylsilyl group, substituted or unsubstituted Aryloxysilyl, substituted or unsubstituted aryl acyl,
  • X is selected from C, O, N, S or Se
  • the undeuterated groups in the above structures may be partially or fully deuterated.
  • said A1 and A2 are each independently selected from the group consisting of:
  • R can be monosubstituted or multisubstituted according to the principle of valence bond, and R is selected from hydrogen, deuterium, halogen, C1 ⁇ C18 alkyl, C1 ⁇ C18 alkoxy, C1 ⁇ C18 alkylsilyl, C1 ⁇ C18 alkane Oxysilyl, C6 ⁇ C40 substituted or unsubstituted aryl, C1 ⁇ C40 heteroaryl, C1 ⁇ C60 substituted or unsubstituted heterospiro, C1 ⁇ C60 substituted or unsubstituted spiro, substituted or unsubstituted Aryl ether group, substituted or unsubstituted heteroaryl ether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilyl group, substituted or Unsubstituted heteroarylsilyl, substituted or unsubstituted hetero
  • X is selected from C, O, N, S or Se
  • Dotted line represents to link to form chemical bond with N and B atom among the formula (I);
  • the undeuterated groups in the above structures may be partially deuterated or fully deuterated.
  • the spiro compound of the present invention is selected from the group consisting of:
  • the present invention also provides a preparation, which comprises a spiro compound and at least one solvent.
  • the solvent is not particularly limited, and unsaturated hydrocarbon solvents (such as toluene, xylene, mesitylene, tetralin, etc.) well known to those skilled in the art can be used.
  • decahydronaphthalene bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc.
  • saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane , bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc.
  • unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, etc.
  • ether solvents such as tetrahydrofuran, tetrahydropyran, etc.
  • ester solvents alkyl benzoate, etc.
  • the present invention also provides an organic photoelectric device, which includes: a first electrode;
  • the organic functional layer contains the spiro compound.
  • the present invention also provides an organic photoelectric device, which comprises a cathode layer, an anode layer and an organic functional layer, the organic functional layer being a hole injection layer, a hole transport layer, a light emitting layer (active layer), a hole blocking layer, an electron injection layer layer and at least one of the electron transport layer, wherein the organic functional layer comprises the spiro compound.
  • the organic functional layer is a light-emitting layer, and the light-emitting layer also contains a host compound, wherein,
  • the volume ratio of the spiro compound to the host compound is 1:1 to 1:99;
  • the host compound is a well-known compound in the art.
  • the present invention also provides a display or lighting device comprising the organic electroluminescent diode.
  • the organic photoelectric element of the present invention is an organic photovoltaic device, an organic electroluminescent device (OLED), an organic solar cell (OSC), an electronic paper (e-paper), an organic photoreceptor (OPC), an organic thin film transistor (OTFT) or an organic Memory device (Organic Memory Element).
  • OLED organic electroluminescent device
  • OSC organic solar cell
  • e-paper electronic paper
  • OPC organic photoreceptor
  • OFT organic thin film transistor
  • OFT organic thin film transistor
  • Organic Memory Element Organic Memory Element
  • the manufacture of the organic photoelectric element of the present invention is as follows: first, metal or conductive oxides and their alloys are deposited on the substrate by methods such as sputter coating, electron beam evaporation, and vacuum evaporation to form an anode; secondly, A hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer and an electron transport layer are sequentially evaporated on the surface of the prepared anode, and finally, a cathode is evaporated.
  • the organic photoelectric element can also be fabricated by vapor deposition on the substrate in the order of cathode, organic functional layer and anode.
  • the organic functional layer is a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport at least one of the layers.
  • the organic functional layer in the present invention can also adopt polymer material according to solvent engineering (spin-coating (spin-coating), thin strip forming (tape-casting), doctor-blading (doctor-blading), screen printing (Screen- Printing), inkjet printing or thermal imaging (Thermal-Imaging), etc.) instead of evaporation methods, can reduce the number of device layers.
  • the organic photoelectric element of the present invention can be classified as top-emitting, bottom-emitting or double-sided emitting according to the materials used.
  • the compounds of the present invention can be applied to electrical devices such as organic solar cells, illuminated OLEDs, flexible OLEDs, organic photoreceptors or organic thin film transistors in a similar principle to organic light-emitting devices.
  • the spiro ring structures introduced in the present invention are perpendicular to the MR-TADF plane skeleton (as shown in Figure 2-5 ), so the tight packing between molecules can be suppressed, and the introduction of the spiro ring structure will not greatly change the energy level of the compound (as shown in Table 1), but it reduces the energy level difference of S1-T1, which is beneficial to the three-line State excitons cross the reverse gap, and the oscillator strength (f) also increases, which finally improves the luminous efficiency of MR-TADF materials and improves the thermal stability of luminescent materials.
  • This kind of spiro compound is applied to organic optoelectronics Devices, especially in organic electroluminescent devices (organic electroluminescent diodes), can improve current efficiency, reduce the operating voltage of components, and obtain long-life organic electroluminescent diodes.
  • the spiro compound of the present invention has good thermal stability, and the introduction of the spiro structure can effectively inhibit the interaction between light-emitting molecules, thereby improving device efficiency.
  • the spiro compound of the present invention has better electron and hole accepting ability, and can improve the energy transmission between the host and the guest.
  • the spiro compound of the present invention is used as an organic functional layer, especially as an effective light-emitting layer.
  • the current efficiency of the electroluminescent device organic electroluminescent diode
  • the lighting voltage is reduced, and the life of the device is greatly improved, indicating that most of the electrons and holes are recombined, and the energy is effectively transferred to the spiro compound. Made to glow, not heat.
  • FIG. 1 is a schematic structural view of an organic electroluminescent diode of the present invention.
  • Figure 2 is a schematic diagram of the HOMO (left) and LUMO (right) hybrid orbitals of compound BN-1;
  • Figure 3 is a schematic diagram of the HOMO (left) and LUMO (right) hybrid orbitals of compound BN-2;
  • Figure 4 is a schematic diagram of the HOMO (left) and LUMO (right) hybrid orbitals of compound BN-3;
  • Figure 5 is a schematic diagram of the HOMO (left) and LUMO (right) hybrid orbitals of compound BN-4.
  • the OLED device of the present invention contains a hole transport layer, and the hole transport material can be preferably selected from known materials, particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures:
  • the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants.
  • the preferred p-type dopant of the present invention is the following structure, but it does not mean that the present invention is limited to the following structure:
  • the electron transport layer contained in the OLED device of the present invention can be selected from at least one of the following compounds, but it does not mean that the present invention is limited to the following structures:
  • the present invention has the general synthetic steps of the compound (guest compound) of structure shown in formula (I) as follows:
  • X is Cl, Br or I.
  • Embodiment 1 the synthesis of compound 1696
  • Embodiment 2 the synthesis of compound 1697
  • Embodiment 3 the synthesis of compound 1698
  • Embodiment 4 the synthesis of compound 1699
  • Embodiment 5 the synthesis of compound 1700
  • Embodiment 6 the synthesis of compound 1701
  • Embodiment 7 the synthesis of compound 1702
  • Embodiment 8 the synthesis of compound 1703
  • Embodiment 9 the synthesis of compound 1704
  • Embodiment 10 the synthesis of compound 1705
  • Embodiment 11 the synthesis of compound 1706
  • Embodiment 12 the synthesis of compound 1707
  • Embodiment 13 the synthesis of compound 1708
  • Embodiment 14 the synthesis of compound 1709
  • the organic electroluminescent diode (bottom emission OLED device) of the present invention comprises substrate 110, anode 120, hole injection layer 130, hole transport layer 140, light-emitting layer 150, hole blocking layer 160, electron Transport layer 170 , electron injection layer 180 and cathode 190 .
  • Each layer of the organic electroluminescent diode of the present invention can be formed by methods such as vacuum evaporation, sputtering, ion plating, or wet film formation such as spin coating, printing, printing, etc.
  • the solvent used is not particularly limited.
  • HT-1 and P-3 are co-evaporated or evaporated to form a 10nm hole injection layer (HIL) (wherein, HT-1 and P -3 with a volume ratio of 95:5), a 90nm hole transport layer (HTL), and then evaporate HT-8 on the hole transport layer to form an electron blocking layer (EBL) with a thickness of 10nm, followed by an electron blocking layer (HTL)
  • HIL hole injection layer
  • HTL 90nm hole transport layer
  • EBL electron blocking layer
  • HTL electron blocking layer
  • EBL electron blocking layer
  • EBL electron blocking layer
  • EML 35nm light-emitting layer
  • ET-13 and LiQ are co-evaporated to form a 35nm electron transport layer (ETL) (wherein, the volume ratio of ET-13 and LiQ is 1:1)
  • Examples 1-9 and Comparative Examples 1-2 were characterized by the same standard methods known in the art. Characteristics such as current efficiency, voltage and lifetime according to the above-mentioned examples and comparative examples are shown in Table 2 below.

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Abstract

本发明公开了一种螺环化合物、制剂、包括该螺环化合物的有机电致发光二极管及显示装置，该螺环化合物的结构如式(I)所示：本发明的螺环化合物具有很好的热稳定性，且将本发明的螺环化合物作为有机功能层，尤其作为发光层制作的有机电致发光二极管，其电流效率提升，起亮电压降低，同时有机电致发光二极管的寿命有较大提升。

Description

螺环化合物、制剂、有机电致发光二极管及显示装置 技术领域
本发明涉及一种螺环化合物，尤其涉及一种螺环化合物和包括该化合物的有机电致发光二极管，属于有机光电领域。
背景技术
有机电致发光二极管(OLED)作为一种新型的显示技术，具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快，适用温度范围广、低驱动电压、可制作柔性可弯曲与透明的显示面板以及环境友好等独特优点，可以应用在平板显示器和新一代照明上，也可以作为LCD的背光源。
20世纪80年代底以来，有机电致发光器件已经在产业上有所应用，OLED发光分为荧光发光和磷光发光两种方式，根据理论推测，由电荷复合形成的单重激发态与三重激发态比例为1:3。小分子荧光材料能利用25％的能量，其余的75％的能量因三重激发态的非发光机制而损失掉，故一般认为荧光材料的内部量子效率极限为25％。2016年Takuji Hatakeyama团队提出了多重共振诱导热活化延迟荧光(MR-TADF)材料设计策略，即利用基于硼和氮原子的多重共振效应引起分子最高占有轨道(HOMO)和分子最低空轨道(LUMO)在不同原子上的分布，实现较小的S1和三重激发态(T1)能级差。同时其刚性的结构限制了分子的振动和转动，抑制激发态结构的扭曲或变形，减少了非辐射弛豫的途径，有利于提高色纯度和发光效率。因此MR-TADF材料展现了高OLED器件效率(最大外量子效率>20％)和高色纯度(半峰宽(FWHM)<30nm)。
目前有机OLED组件中的发光层几乎全部使用主客体发光体系机构，即在主体材料中掺杂客体发光材料，一般来说，有机主体材料的能系要比客体材料大，即能量由主体传递给客体，使客体材料被激发而发光。目前MR-TADF开始应用于商业OLED材料，但仍然存在一些技术难点，比如OLED要求效率高，寿命长，操作电压更低。由于MR-TADF分子的骨架为平面结构，在固态条件下易于发生分子堆叠，而发光分子间的强相互作用易引起聚集诱导的荧光淬灭，从而降低MR-TADF OLED器件发光效率。
因此，有必要开发一种新型的有机化合物，且包含该有机化合物的有机电致发光二极管具有较好的效率、较高的寿命及降低的驱动电压。
发明内容
为了克服现有技术中存在的缺陷，本发明的目的是提供一种螺环化合物及包含该螺环化合物的有机电致发光二极管，该有机电致发光二极管具有较好的效率、较高的寿命及降低的驱动电压。
为了实现本发明的目的，本发明的技术方案如下：
本发明提供了螺环化合物，其结构如式(I)示：
Figure PCTCN2022075574-appb-000001
Figure PCTCN2022075574-appb-000002
其中，A 1和A 2各自独立地选自由以下组成的群组：
Figure PCTCN2022075574-appb-000003
其中，B1、B2、B3、B4、C1、C2和D1各自独立地选自C6～C60的芳基或C1～C60的杂芳基；
B1、B2、B3、B4、C1、C2和D1可以根据价键原则进行单取代或多取代；
X选自C、O、N、S或Se；
虚线表示与式(I)中N和B原子相连形成化学键。
R 1、R和R 2各自独立地选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；
上述结构中未被氘代的基团，可以被部分或全部氘代。
优选地，所述的B1、B2、B3和B4各自独立地选自由以下组成的群组：
Figure PCTCN2022075574-appb-000004
其中，R独立地选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；X选自C、O、N、S或Se；
上述结构中未被氘代的基团，可以被部分或全部氘代。
更优选地，所述的C1和C2各自独立地选自下列结构：
Figure PCTCN2022075574-appb-000005
其中，R选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；
X选自C、O、N、S或Se；
上述结构中未被氘代的基团，可以被部分或全部氘代；
虚线表示与上述结构中的六元环相连形成化学键。
更优选地，所述的D1选自下列结构：
Figure PCTCN2022075574-appb-000006
其中，R选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～ C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；
X选自C、O、N、S或Se；
上述结构中未被氘代的基团，可以被部分或全部氘代。
更优选地，所述的A 1和A 2各自独立地选自由以下组成的群组：
Figure PCTCN2022075574-appb-000007
Figure PCTCN2022075574-appb-000008
Figure PCTCN2022075574-appb-000009
其中，R可根据价键原则进行单取代或多取代，R选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基；其中，n为0到10的整数；
X选自C、O、N、S或Se；
虚线表示与式(I)中N和B原子相连形成化学键；
上述结构中未被氘代的基团可被部分氘代或全氘代。
更优选地，本发明的螺环化合物选自由以下组成的群组：
Figure PCTCN2022075574-appb-000010
Figure PCTCN2022075574-appb-000011
Figure PCTCN2022075574-appb-000012
Figure PCTCN2022075574-appb-000013
Figure PCTCN2022075574-appb-000014
Figure PCTCN2022075574-appb-000015
Figure PCTCN2022075574-appb-000016
Figure PCTCN2022075574-appb-000017
Figure PCTCN2022075574-appb-000018
Figure PCTCN2022075574-appb-000019
Figure PCTCN2022075574-appb-000020
Figure PCTCN2022075574-appb-000021
Figure PCTCN2022075574-appb-000022
Figure PCTCN2022075574-appb-000023
Figure PCTCN2022075574-appb-000024
Figure PCTCN2022075574-appb-000025
Figure PCTCN2022075574-appb-000026
Figure PCTCN2022075574-appb-000027
Figure PCTCN2022075574-appb-000028
Figure PCTCN2022075574-appb-000029
Figure PCTCN2022075574-appb-000030
Figure PCTCN2022075574-appb-000031
Figure PCTCN2022075574-appb-000032
Figure PCTCN2022075574-appb-000033
Figure PCTCN2022075574-appb-000034
Figure PCTCN2022075574-appb-000035
Figure PCTCN2022075574-appb-000036
Figure PCTCN2022075574-appb-000037
Figure PCTCN2022075574-appb-000038
Figure PCTCN2022075574-appb-000039
Figure PCTCN2022075574-appb-000040
Figure PCTCN2022075574-appb-000041
Figure PCTCN2022075574-appb-000042
Figure PCTCN2022075574-appb-000043
Figure PCTCN2022075574-appb-000044
Figure PCTCN2022075574-appb-000045
Figure PCTCN2022075574-appb-000046
Figure PCTCN2022075574-appb-000047
Figure PCTCN2022075574-appb-000048
Figure PCTCN2022075574-appb-000049
Figure PCTCN2022075574-appb-000050
本发明还提供了制剂，其包含螺环化合物和至少一种溶剂，该溶剂没有特别限制，可以使用本领域技术人员公知的不饱和烃溶剂(例如甲苯、二甲苯、均三甲苯、四氢化萘、十氢萘、双环己烷、正丁基苯、仲丁基苯、叔丁基苯等)、饱和烃溶剂(例如四氯化碳、氯仿、二氯甲烷、二氯乙烷、氯丁烷、溴丁烷、氯戊烷、溴戊烷、氯己烷、溴己烷、氯环己烷、溴环己烷等)、不饱和烃溶剂(例如氯苯、二氯苯、三氯苯等)、醚类溶剂(例如四氢呋喃、四氢吡喃等)和酯类溶剂(苯甲酸烷基酯等)。该制剂直接用于制备有机电致发光二极管。
本发明还提供了有机光电器件，其包括：第一电极；
第二电极，与所述第一电极相面对；
有机功能层，夹设于所述第一电极和所述第二电极之间；
其中，有机功能层包含该螺环化合物。
本发明还提供了有机光电器件，其包括阴极层、阳极层和有机功能层，该有机功能层为空穴注入层、空穴传输层、发光层(活性层)、空穴阻挡层、电子注入层和电子传输层中至少一者，其中该有机功能层包含该螺环化合物。
优选地，该有机功能层为发光层，该发光层中还包含主体化合物，其中，
该螺环化合物与该主体化合物的体积比为1：1～1：99；
该主体化合物为本领域公知的化合物。
本发明还提供了显示或照明装置，其包括该有机电致发光二极管。
本发明的有机光电元件是有机光伏器件、有机电致发光器件(OLED)、有机太阳电池(OSC)、电子纸(e-paper)、有机感光体(OPC)、有机薄膜晶体管(OTFT)或有机内存器件(Organic Memory Element)。
本发明的有机光电元件的制作如下：首先，通过喷溅涂覆法、电子束蒸发、真空蒸镀等方法在基板上蒸镀金属或具有导电性的氧化物以及它们的合金形成阳极；其次，在制备得到的阳极表面按顺序蒸镀空穴注入层、空穴传输层、发光层、空穴阻挡层和电子传输层，最后后，蒸镀阴极。除了上述方法，在基板上也可按阴极、有机功能层及阳极顺序蒸镀制作有机光电 元件，该有机功能层为空穴注入层、空穴传输层、发光层、空穴阻挡层及电子传输层中至少一层。本发明中的有机功能层也可以采用高分子材料按溶剂工程(旋转涂膜(spin-coating)、薄带成型(tape-casting)、刮片法(doctor-blading)、丝网印刷(Screen-Printing)、喷墨印刷或热成像(Thermal-Imaging)等)替代蒸镀方法制备，可以减少器件层数。
本发明的有机光电元件根据所使用的材料可以归类为顶发射、底发射或双面发射。本发明的化合物可以有机发光器件类似的原理应用于有机太阳能电池、照明的OLED、柔性OLED、有机感光体或有机薄膜晶体管等电致器件。
本发明通过改变MR-TADF发光材料的结构，引入特定的大位阻螺环结构、取代基等，由于本发明中引入的螺环结构垂直于MR-TADF平面骨架(如图2-5所示)，因此可以抑制分子间的紧密堆积，同时引入螺环结构并不会很大程度上改变化合物的能级(如表1所示)，但是减小了S1-T1的能级差，有利于三线态激子发生反向隙间穿越，另外振子强度(f)也增大了，最终改善了MR-TADF材料的发光效率，提升发光材料的热稳定性，将此类螺环化合物应用于有机光电器件，特别是在有机电致发光器件(有机电致发光二极管)中，可以提升电流效率、降低元器件的操作电压，获得长寿命的有机电致发光二极管。
表1
Figure PCTCN2022075574-appb-000051
本发明的有益效果：
本发明的螺环化合物具有很好的热稳定性，通过引入螺环结构，可以有效抑制发光分子间的相互作用，从而提高器件效率。本发明的螺环化合物具有较好的电子和空穴接收能力，可提升主体和客体之间的能量传输，具体表现为用本发明的螺环化合物作为有机功能层，尤其作为发光层制作的有机电致发光器件(有机电致发光二极管)其电流效率提升，起亮电压降低，同时器件的寿命有较大提升，说明大部分电子和空穴复合后，能量都有效地传递给该螺环化合物用于发光，而非发热。
附图说明
图1为本发明的有机电致发光二极管的结构示意图。
图2为化合物BN-1的HOMO(左)和LUMO(右)杂化轨道示意图；
图3为化合物BN-2的HOMO(左)和LUMO(右)杂化轨道示意图；
图4为化合物BN-3的HOMO(左)和LUMO(右)杂化轨道示意图；
图5为化合物BN-4的HOMO(左)和LUMO(右)杂化轨道示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合具体实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明的OLED器件中含有空穴传输层，且空穴传输材料可以优选自公知的材料，特别优选地选自以下结构，但并不代表本发明限于以下结构：
Figure PCTCN2022075574-appb-000052
本发明的OLED器件中含有的空穴传输层，其包含一种或多种p型掺杂剂。本发明优选的p型掺杂剂为以下结构，但并不代表本发明限于以下结构：
Figure PCTCN2022075574-appb-000053
本发明的OLED器件中含有的电子传输层可以选自以下化合物中的至少一者，但并不代表本发明限于以下结构：
Figure PCTCN2022075574-appb-000054
下列对比例中采用化合物BN-1和BN-2以及本发明的代表化合物BN-3和BN-4的结构如下：
Figure PCTCN2022075574-appb-000055
本发明具有式(I)所示结构的化合物(客体化合物)的通用合成步骤如下：
Figure PCTCN2022075574-appb-000056
其中X为Cl、Br或I。
Figure PCTCN2022075574-appb-000057
通用合成步骤，
在氩气保护下，将化合物A(0.10摩尔)、叔丁基锂(0.2摩尔)和叔丁基苯(100毫升)的混合溶液在-40度反应4小时，完成后升温80度，再反应4小时，滴加BBr 3(0.2摩尔)，滴加完成后升温80度，反应4小时，然后滴加EtN(i-Pr) 2(0.30摩尔),滴加完成后回流过夜。停止加热，降至室温，加入适量的蒸馏水。在减压条件下除去溶剂，固体溶解在二氯甲烷中，过硅胶短柱。得到最终目标产品。收率21～58％。
在氩气保护下，将化合物B(0.10摩尔)、BBr 3(0.2摩尔)、EtN(i-Pr) 2(0.30摩尔)、叔丁基苯(100毫升)的混合溶液回流加热48小时。停止加热，降至室温，加入适量的蒸馏水。在减压条件下除去溶剂，固体溶解在二氯甲烷中，过硅胶短柱。得到最终目标产品。收率20～51％。结合以下实施例详细地解释了该螺环化合物(即客体化合物)的制备方法以及器件的发光性能，化合物A和化合物B通过本领域公知的方法合成获得。但这些仅仅用于举例描述本发明的实施方式，所以本发明的范围并不限于此。
实施例1：化合物1696的合成
Figure PCTCN2022075574-appb-000058
参考上述通用合成步骤，终产物的产率为35％。质谱m/z,理论值1104.56；实测值M+H：1105.6。
实施例2：化合物1697的合成
Figure PCTCN2022075574-appb-000059
参考上述通用合成步骤，终产物的产率为31％。质谱m/z,理论值980.53；实测值M+H：981.6。
实施例3：化合物1698的合成
Figure PCTCN2022075574-appb-000060
参考上述通用合成步骤，终产物的产率为33％。质谱m/z,理论值1090.54；实测值M+H：1091.6。
实施例4：化合物1699的合成
Figure PCTCN2022075574-appb-000061
参考上述通用合成步骤，终产物的产率为34％。质谱m/z,理论值902.48；实测值M+H：903.5。
实施例5：化合物1700的合成
Figure PCTCN2022075574-appb-000062
参考上述通用合成步骤，终产物的产率为41％。质谱m/z,理论值888.46；实测值M+H：889.5。
实施例6：化合物1701的合成
Figure PCTCN2022075574-appb-000063
参考上述通用合成步骤，终产物的产率为32％。质谱m/z,理论值939.48；实测值M+H：940.5。
实施例7：化合物1702的合成
Figure PCTCN2022075574-appb-000064
Figure PCTCN2022075574-appb-000065
参考上述通用合成步骤，终产物的产率为30％。质谱m/z,理论值940.47；实测值M+H：941.5。
实施例8：化合物1703的合成
Figure PCTCN2022075574-appb-000066
参考上述通用合成步骤，终产物的产率为27％。质谱m/z,理论值1103.33；实测值M+H：1104.4。
实施例9：化合物1704的合成
Figure PCTCN2022075574-appb-000067
参考上述通用合成步骤，终产物的产率为29％。质谱m/z,理论值1050.61；实测值M+H：1051.7。
实施例10：化合物1705的合成
Figure PCTCN2022075574-appb-000068
参考上述通用合成步骤，终产物的产率为25％。质谱m/z,理论值994.45；实测值M+H：994.5。
实施例11：化合物1706的合成
Figure PCTCN2022075574-appb-000069
参考上述通用合成步骤，终产物的产率为35％。质谱m/z,理论值978.48；实测值M+H：978.5。
实施例12：化合物1707的合成
Figure PCTCN2022075574-appb-000070
参考上述通用合成步骤，终产物的产率为31％。质谱m/z,理论值984.52；实测值M+H：985.6。
实施例13：化合物1708的合成
Figure PCTCN2022075574-appb-000071
参考上述通用合成步骤，终产物的产率为29％。质谱m/z,理论值984.52；实测值M+H：984.6。
实施例14：化合物1709的合成
Figure PCTCN2022075574-appb-000072
参考上述通用合成步骤，终产物的产率为30％。质谱m/z,理论值1004.49；实测值M+H：1005.5。
器件实施例
如图1所示，本发明的有机电致发光二极管(底发射OLED器件)包括基板110、阳极120、空穴注入层130、空穴传输层140、发光层150、空穴阻挡层160、电子传输层170、电子注入层180和阴极190。本发明有机电致发光二极管的各层可采用真空蒸镀、溅射、离子电镀等方法，或湿法成膜如旋涂、打印、印刷等方法形成，所用的溶剂没有特别限制。
实施例1-9中OLED器件的制造：
在发光面积为2mm×2mm大小的ITO玻璃的表面或阳极上将HT-1与P-3共蒸或者蒸镀HT-1形成10nm的空穴注入层(HIL)(其中，HT-1与P-3的体积比为95:5)，90nm的空穴传输层(HTL)，接着在空穴传输层上蒸镀HT-8，形成厚度为10nm的电子阻挡层(EBL)，随后在电子阻挡层上将本领域公知的主体材料(例如BH-1)与本发明的螺环化合物(化合物1-11)(客体材料)共蒸形成35nm的发光层(EML)(其中，该螺环化合物与主体化合物的体积比为3:97)，最后用ET-13与LiQ共蒸形成35nm的电子传输层(ETL)(其中，ET-13与LiQ的体积比为1:1)，然后蒸镀阴极Al 70nm，从而制造了有机电致发光二极管。
对比例1-2中OLED器件的制造：
对比例1-2中OLED器件的制造与实施例1-9类似，区别仅在于对比例1-2中采用BN-1～BN-2(作为发光层的客体材料)替代本发明的螺环化合物(化合物1-11)。
Figure PCTCN2022075574-appb-000073
实施例1-9与对比例1-2中的有机电致发光二极管通过本领域公知的相同的标准方法表征。依据上述实施例和对比例电流效率、电压和寿命等特性显示在下表2中。
表2
Figure PCTCN2022075574-appb-000074
由表1可以看出，从在配体结构上并入稠环，实施例1至实施例5展示了良好的器件性能，说明本发明的螺环化合物具有一定的应用价值。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 螺环化合物，所述的螺环化合物的结构如式(I)所示：
    Figure PCTCN2022075574-appb-100001
    其中，A 1和A 2各自独立地选自由以下组成的群组：
    Figure PCTCN2022075574-appb-100002
    其中，B1、B2、B3、B4、C1、C2和D1各自独立地选自C6～C60的芳基或C1～C60的杂芳基；B1、B2、B3、B4、C1、C2和D1可以进行单取代或多取代；
    X选自C、O、N、S或Se；
    虚线表示与式(I)中N和B原子相连形成化学键；
    R 1、R和R 2各自独立地选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10 的整数；
    上述结构中未被氘代的基团，可以被部分或全部氘代。
  2. 根据权利要求1所述的螺环化合物，其中，所述的B1、B2、B3和B4各自独立地选自由以下组成的群组：
    Figure PCTCN2022075574-appb-100003
    其中，R独立地选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；X选自C、O、N、S或Se；
    上述结构中未被氘代的基团，可以被部分或全部氘代。
  3. 根据权利要求1或2所述的螺环化合物，其中，所述的C1和C2各自独立地选自下列结构：
    Figure PCTCN2022075574-appb-100004
    其中，R选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；
    X选自C、O、N、S或Se；
    虚线表示与权利要求2中所述的六元环相连形成化学键；
    上述结构中未被氘代的基团，可以被部分或全部氘代。
  4. 根据权利要求1或2所述的螺环化合物，其中，所述的D1选自下列结构：
    Figure PCTCN2022075574-appb-100005
    其中，R选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；
    X选自C、O、N、S或Se；
    上述结构中未被氘代的基团，可以被部分或全部氘代。
  5. 根据权利要求1或2所述的螺环化合物，其中，所述的A 1和A 2各自独立地选自由以下组成的群组：
    Figure PCTCN2022075574-appb-100006
    Figure PCTCN2022075574-appb-100007
    Figure PCTCN2022075574-appb-100008
    Figure PCTCN2022075574-appb-100009
    其中，R选自氢、氘、卤素、C1～C18烷基、C1～C18烷氧基、含C1～C18烷硅基、含C1～C18烷氧硅基、C6～C40取代或未取代的芳基，C1～C40的杂芳基、C1～C60取代或未取代的杂螺环、C1～C60取代或未取代的螺环、取代或未取代的芳基醚基、取代或未取代的杂芳基醚基、取代或未取代的芳基胺基、取代或未取代的杂芳基胺基、取代或未取代的芳基硅基、取代或未取代的杂芳基硅基、取代或未取代的芳基氧硅基、取代或未取代的芳基酰基、取代或未取代的杂芳基酰基或取代或未取代的氧膦基，其中，n为0到10的整数；
    X选自C、O、N、S或Se；
    虚线表示与式(I)中N和B原子相连形成化学键；
    上述结构中未被氘代的基团可被部分氘代或全氘代。
  6. 根据权利要求1或2所述的螺环化合物，其中，所述的螺环化合物选自由以下组成的群组：
    Figure PCTCN2022075574-appb-100010
    Figure PCTCN2022075574-appb-100011
    Figure PCTCN2022075574-appb-100012
    Figure PCTCN2022075574-appb-100013
    Figure PCTCN2022075574-appb-100014
    Figure PCTCN2022075574-appb-100015
    Figure PCTCN2022075574-appb-100016
    Figure PCTCN2022075574-appb-100017
    Figure PCTCN2022075574-appb-100018
    Figure PCTCN2022075574-appb-100019
    Figure PCTCN2022075574-appb-100020
    Figure PCTCN2022075574-appb-100021
    Figure PCTCN2022075574-appb-100022
    Figure PCTCN2022075574-appb-100023
    Figure PCTCN2022075574-appb-100024
    Figure PCTCN2022075574-appb-100025
    Figure PCTCN2022075574-appb-100026
    Figure PCTCN2022075574-appb-100027
    Figure PCTCN2022075574-appb-100028
    Figure PCTCN2022075574-appb-100029
    Figure PCTCN2022075574-appb-100030
    Figure PCTCN2022075574-appb-100031
    Figure PCTCN2022075574-appb-100032
    Figure PCTCN2022075574-appb-100033
    Figure PCTCN2022075574-appb-100034
    Figure PCTCN2022075574-appb-100035
    Figure PCTCN2022075574-appb-100036
    Figure PCTCN2022075574-appb-100037
    Figure PCTCN2022075574-appb-100038
    Figure PCTCN2022075574-appb-100039
    Figure PCTCN2022075574-appb-100040
    Figure PCTCN2022075574-appb-100041
    Figure PCTCN2022075574-appb-100042
    Figure PCTCN2022075574-appb-100043
    Figure PCTCN2022075574-appb-100044
    Figure PCTCN2022075574-appb-100045
    Figure PCTCN2022075574-appb-100046
    Figure PCTCN2022075574-appb-100047
    Figure PCTCN2022075574-appb-100048
    Figure PCTCN2022075574-appb-100049
  7. 制剂，其包含权利要求1或2所述的螺环化合物和至少一种溶剂，其中，所述溶剂为饱和烃溶剂、不饱和烃溶剂、醚类溶剂或酯类溶剂。
  8. 有机电致发光二极管，其包括阴极层、阳极层和有机功能层，所述有机功能层为空穴注入层、空穴传输层、发光层、空穴阻挡层、电子注入层和电子传输层，其中，所述有机功能层包含权利要求1或2所述的螺环化合物。
  9. 根据权利要求8所述的有机电致发光二极管，其中，所述有机功能层为发光层，所述发光层中还包含主体化合物，其中，
    所述螺环化合物与所述主体化合物的体积比为1：1～1：99。
  10. 显示装置，其包括权利要求8所述的有机电致发光二极管。
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CN116874517A (zh) * 2023-09-08 2023-10-13 浙江华显光电科技有限公司 含硒吩化合物及其在有机发光装置的应用
CN116874517B (zh) * 2023-09-08 2023-12-01 浙江华显光电科技有限公司 含硒吩化合物及其在有机发光装置的应用
CN117946146A (zh) * 2024-03-27 2024-04-30 浙江华显光电科技有限公司 含咪唑及衍生基团的硼氮化合物、有机电致发光器件及应用

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