CN113666936A - Photopolymerizable imide diene discotic liquid crystal of triaza-triindene thiophene bridged carbazole and application of photopolymerizable imide diene discotic liquid crystal in organic electronic devices - Google Patents

Photopolymerizable imide diene discotic liquid crystal of triaza-triindene thiophene bridged carbazole and application of photopolymerizable imide diene discotic liquid crystal in organic electronic devices Download PDF

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CN113666936A
CN113666936A CN202110810611.2A CN202110810611A CN113666936A CN 113666936 A CN113666936 A CN 113666936A CN 202110810611 A CN202110810611 A CN 202110810611A CN 113666936 A CN113666936 A CN 113666936A
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胡光
凌志强
丁师杰
胡伟伟
张开龙
孔亚州
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Huaiyin Institute of Technology
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Abstract

The invention belongs to the technical field of organic synthetic materials, and discloses a photopolymerizable imide diene discotic liquid crystal of triaza triindacene thiophene bridged carbazole and application thereof in an organic electronic device, wherein the photopolymerizable imide diene discotic liquid crystal of triaza triindacene thiophene bridged carbazole is shown in a general formula (I); a mixture comprising at least one compound according to claim 1 or a polymer according to claim 2 and at least one further organic functional material. The excellent hole/electron transmission performance, the chemically stable photopolymerisable imide diene group, the large-plane conjugated triazatriindene and carbazole aromatic structures among the disc layers of the discotic liquid crystal are connected through thiophene, so that better carrier transmission and photoelectric response are realized, better energy level matching is realized, the photoelectric performance and stability of the compound and a photoelectric device are improved, and a material solution for manufacturing a light-emitting device with high efficiency and long service life is provided.

Description

Photopolymerizable imide diene discotic liquid crystal of triaza-triindene thiophene bridged carbazole and application of photopolymerizable imide diene discotic liquid crystal in organic electronic devices
Technical Field
The invention relates to the technical field of organic synthetic materials, in particular to a photopolymerizable imide diene discotic liquid crystal of triazatriindene thiophene bridged carbazole, a composition and a mixture containing the same, and application of the photopolymerizable imide diene discotic liquid crystal in an organic electronic device.
Background
Due to the characteristics of diversity of molecular structure design, relatively low manufacturing cost, excellent photoelectric performance and the like, the organic semiconductor material has great application potential in a plurality of photoelectric devices, such as Organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), Organic Field Effect Transistors (OFETs) and the like. Organic semiconductor materials have gained rapid development in the field of flat panel displays and lighting, since the bilayer OLED structure was reported in, inter alia, dun kun et al (c.w.tang and s.a.van Slyke, appl.phys.lett.,1987,51,913) in 1987.
The organic thin film light emitting element must satisfy enhancement of light emitting efficiency, reduction of driving voltage, enhancement of durability, and the like. However, there are still many technical issues, wherein the high efficiency and long lifetime of the device are one of the difficulties.
In order to accelerate the process of promoting the large-scale industrialization of the OLED and improve the photoelectric property of the OLED, various novel organic photoelectric material systems are widely designed, developed and produced. Among them, carbazole organic semiconductor materials have been widely used in optoelectronic devices due to their excellent photoelectric properties, redox properties, stability, etc. In addition, the liquid crystal promotes the carrier transport property and the light emitting property of the semiconductor material in its excellent molecular arrangement mode. However, the currently reported non-liquid crystal and non-amide diene polymerizable structure tricarbazole materials have certain limitations in carrier transport capability, stability, service life and the like in photoelectric devices.
In addition, in order to reduce production costs and realize large area OLED devices, printing OLEDs is becoming one of the most promising technology options. For this, printing OLED materials is critical. The photopolymerisable material is an ideal hole/electron transport layer material for solution processing printing of the OLED, can avoid the problem of poor solubility of polymers, realizes in-situ crosslinking, and can also avoid the defect that small molecular materials are easy to be washed away by solvents in a coating process. In addition, the ordered molecular arrangement mode of the liquid crystal material, particularly the small interlayer spacing among the disc layers of the discotic liquid crystal, is beneficial to realizing high carrier transport performance. However, the currently developed small molecule OLED materials have poor solubility and film forming property due to their low molecular weight and rigid aromatic molecular structure, and especially it is difficult to form a void-free amorphous thin film with regular morphology.
In organic semiconductor materials, the transport of holes and electrons is achieved by the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) of highly conjugated aromatic molecules. The absorption and emission of light is generally excited by electron transfer between the HOMO and LUMO, i.e. the generation and dissociation of excitons (combined hole-electron pairs). Charge transport and light emission depend not only on the energy and wave functions of the molecular orbitals, but also critically on the molecular packing arrangement, e.g., the morphology of the film. Studies (adv. mater.2011,23,566) have shown that the same material, due to differences in molecular arrangement and phase states in organic opto-electronic devices, can exhibit carrier mobilities that differ by orders of magnitude. In general, the high degree of regular order present in crystalline organic semiconductor thin films results in high carrier mobility, and certain crystals also exhibit high luminous efficiency. However, interfaces between domains (lattice defects) often result in charge trapping quenching, affecting device efficiency. Furthermore, such regular molecular arrangement and phase structure may lead to unwanted molecular clustering, which may also cause quenching luminescence or shift of the spectrum. On the other hand, although amorphous organic semiconductors may be efficient emitters and have good processability, they generally exhibit relatively limited charge carrier mobility. Therefore, a desirable high mobility organic semiconductor should have both good molecular order and few lattice defects and agglomerates, such as liquid crystals. Liquid crystal refers to a class of materials that have the ability to both flow as a liquid and retain the anisotropic character of crystalline molecules over a range of temperatures or in some solvent conditions. The liquid crystal molecular arrangement is between the crystalline state of a completely regular structure and the completely disordered liquid state, and self-assembly through the formation of a liquid crystal phase is a key strategy for controlling the ordered accumulation of the organic semiconductor and inhibiting the formation of defects. The liquid crystal material can be annealed in the mesophase and locked into a highly uniform molecular orientational order by subsequent crystallization, vitrification formation or cross-linking of adjacent molecules into a non-melt insoluble polymer network. One key advantage of liquid crystallinity is the ability to form single domain samples without lattice defects due to the grain barrier between adjacent domains.
Professor Mullen, Maplen, Germany (adv.Mater.,1999,11, 1469; adv.Mater.,2005,17, 684; adv.Mater.,2008,20,2715), professor Adam, university of Bayer, Germany (Nature,1994,371,141), professor Friend, Cambridge university, England, and professor Oxford Bradley (appl.Phys.Lett.,2000,77,406), etc., all report a series of small liquid crystal molecules and liquid crystal polymers for use in flexible electronic devices, achieving good charge transport and luminescence properties. However, these reported small molecule liquid crystals and high polymer liquid crystals have limitations in realizing large-scale, low-cost, high-efficiency, solution-printed, fully flexible electronic device applications. Small molecule materials can be sublimed and evaporated, but are easily washed away by solvents, making it difficult to use low cost solution processes. The polymer material has the problems of difficult dissolution, difficult purification and the like, and directly influences the manufacturing process and the film forming quality of the solution method.
Therefore, designing and synthesizing functional compounds with liquid crystal performance, photopolymerisable performance, good photoelectric performance, solubility and film-forming performance is very important for realizing the organic light-emitting diode processed by high-performance solution.
Disclosure of Invention
The invention aims to provide a novel organic photoelectric material, in particular to photopolymerizable imide diene discotic liquid crystal based on triazatriindene thiophene bridged carbazole, a mixture and a composition containing the same, and application of the photopolymerizable imide diene discotic liquid crystal in an organic electronic device, aiming at reducing driving voltage, improving luminous efficiency, stability and device life, solving the problems of poor carrier transport capacity, stability and short service life of the existing organic electronic device, and simultaneously providing a material solution for printing OLED (organic light emitting diode), and effectively solving the problems provided in the background technology.
In order to achieve the purpose, the invention adopts the technical scheme that:
a photopolymerizable imide diene discotic liquid crystal of triazatriindane thiophene bridged carbazole of general formula (I):
Figure BDA0003168076510000041
wherein the content of the first and second substances,
R1the multiple occurrences, which may be the same or different, may be H, D, F, -CN, -NO2、-CF3An alkenyl group, an alkynyl group, an amino group, an acyl group, an amide group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 60 carbon atoms, a substituted or unsubstituted heterocyclic aromatic group having 3 to 60 carbon atoms, a substituted or unsubstituted fused ring aromatic group having 7 to 60 carbon atoms, or a carbon atom number4 to 60 fused heterocyclic aromatic groups, or an aliphatic or aromatic ring system wherein one or more groups may form a mono-or polycyclic ring with each other and/or with said groups;
R2the multiple occurrences, which may be the same or different, may be H, D, F, -CN, -NO2、-CF3Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfone, substituted or unsubstituted alkyl of 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 60 carbon atoms, substituted or unsubstituted aromatic group of 6 to 60 carbon atoms, substituted or unsubstituted heterocyclic aromatic group of 3 to 60 carbon atoms, substituted or unsubstituted fused ring aromatic group of 7 to 60 carbon atoms, or fused ring aromatic group of 4 to 60 carbon atoms, or a ring-shaped aliphatic or aromatic ring system in which one or more groups may be bonded to each other and/or to the group to form a single ring or multiple rings;
r3 is the same or different at multiple occurrences and may be H, D, F, -CN, -NO2, -CF3, alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfone, substituted or unsubstituted alkyl of 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 60 carbon atoms, substituted or unsubstituted aromatic group of 6 to 60 carbon atoms, substituted or unsubstituted heterocyclic aromatic group of 3 to 60 carbon atoms, substituted or unsubstituted fused ring aromatic group of 7 to 60 carbon atoms, or fused ring aromatic group of 4 to 60 carbon atoms, or an aliphatic or aromatic ring system in which one or more groups may form a single ring or multiple rings with each other and/or with the ring to which the groups are bonded.
A high polymer comprises at least one repeating structural unit shown as a general formula (I).
A mixture comprising at least one compound according to claim 1 or a polymer according to claim 2 and at least one further organic functional material selected from the group consisting of hole (also called hole) injection or transport materials (HIM/HTM), Hole Blocking Materials (HBM), electron injection or transport materials (EIM/ETM), Electron Blocking Materials (EBM), organic matrix materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermal emission delayed fluorescent materials (TADF materials) and organic dyes.
A composition comprising at least one compound according to claim 1 or polymer according to claim 2, and at least one organic solvent.
An organic electronic device comprising an organic compound according to claim 1 or a high polymer according to claim 2.
Preferably, the Organic electronic device is selected from Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronic devices, Organic sensors and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes).
Further comprising a hole transporting or injecting layer comprising a compound according to claim 1 or a polymer according to claim 2.
A method for preparing a functional layer by applying a compound according to claim 1 onto a substrate by evaporation, or by co-evaporation with at least one other organic functional material, or by applying a composition according to claim 4 onto a substrate by Printing or coating, wherein the Printing or coating is selected from ink-jet Printing, jet Printing (Nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexography, web Printing, spray coating, brush coating or pad Printing, and slot die coating.
Compared with the prior art, the invention has the following beneficial effects:
the excellent hole/electron transmission performance, the chemically stable photopolymerisable imide diene group, the large-plane conjugated triazatriindene and carbazole aromatic structures among the disc layers of the discotic liquid crystal are connected through thiophene, so that better carrier transmission and photoelectric response are realized, better energy level matching is realized, the photoelectric performance and stability of the compound and a photoelectric device are improved, and a material solution for manufacturing a light-emitting device with high efficiency and long service life is provided;
secondly, the photopolymerisable liquid crystal is applied to a flexible electronic device processed by solution, so that the good solubility of small molecular materials is realized, the film is formed by a solution method, the in-situ polymerization is adopted, the infusible and insoluble polymer network thin film layer is realized, the liquid crystal phase state molecular orientation order with uniform height can be locked without being washed away by a new printing layer solvent;
and thirdly, the imide diene with more stable and higher photopolymerization efficiency is adopted to replace the traditional ester diene, so that higher in-situ polymerization efficiency is realized. The invention also introduces a large-plane conjugated triazatriindene and carbazole aromatic structure into the discotic liquid crystal system, thereby realizing better energy level matching, carrier transmission and luminescence property.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Examples of preferred compounds according to the invention are listed below, but not limited to the following structures:
Figure BDA0003168076510000071
Figure BDA0003168076510000081
Figure BDA0003168076510000091
Figure BDA0003168076510000101
in a preferred embodiment, the light-emitting device according to the present invention comprises a hole transport layer or a hole injection layer comprising the highly conjugated photopolymerizable imide diene liquid crystal material of the present invention.
The light-emitting device according to the present invention emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.
The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
Example 1
Synthesis of compound triazatriindene thiophene bridged carbazole imide diene discotic liquid crystal (6):
Figure BDA0003168076510000111
synthesis of intermediate (2)
A100 ml three-necked flask was charged with intermediate (1) (10.00g,47.17mmol) and phosphorus oxychloride (50 cm) under nitrogen atmosphere3) Then, the mixture was heated to 100 ℃ and the system was kept reacting for 12 hours. After cooling, the mixture was carefully poured slowly into a solid ice bath and the pH was adjusted to 7-8 with potassium hydroxide. After neutralization, filtration gave a brown initial product. Purification by column chromatography (ethyl acetate/n-hexane ═ 2:10) and recrystallization afforded a pale yellow solid, intermediate (2) in 65% yield.
Synthesis of intermediate (4)
Taking brominated intermediate (2) (10g,17.18mmol) and boric acid intermediate (3) (27.50g,51.54mmol) in a 500ml double-neck round-bottom flask under the protection of nitrogen, adding 250ml of toluene as a solvent, installing a device, taking potassium carbonate (7.11g, 51.54mmol), completely dissolving the potassium carbonate with 30ml of water, adding the potassium carbonate into the round-bottom flask, and finally taking Pd (PPh)3)4(1.00g, 0.86mmol) in a flask, the air in the flask was evacuated with an oil pump,introducing nitrogen, heating at constant temperature, refluxing for reaction for 12 hours, and cooling. The reaction solution was transferred to a rotary evaporation flask, most of the solvent was rotary evaporated, extracted with dichloromethane, washed three times with water, dried over anhydrous magnesium sulfate, filtered, rotary dried, and purified to give intermediate (4) in 78% yield.
Synthesis of triaza-triindene thiophene bridged carbazole imide diene discotic liquid crystal (6)
Intermediate (4) (10g, 5.53mmol) and potassium hydroxide (3.1g,55.3mmol) were heated to reflux in 50ml of tetrahydrofuran under nitrogen blanket for one hour. Brominated intermediate (5) (5.58g, 16.6mmol) was then added slowly and the resulting mixture was heated to reflux for an additional 12 hours. And (3) after cooling, transferring the reaction liquid into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain the triazatriindene thiophene bridged carbazole imide diene discotic liquid crystal (4) with the yield of 76%.
Example 2
Synthesis of compound triazatriindene thiophene bridged carbazole imide diene discotic liquid crystal (8):
Figure BDA0003168076510000121
intermediate (4) (10g, 5.53mmol) and potassium hydroxide (3.1g,55.3mmol) were heated to reflux in 50ml of tetrahydrofuran under nitrogen blanket for one hour. Brominated intermediate (7) (6.01g, 16.6mmol) was then added slowly and the resulting mixture was heated to reflux for an additional 12 hours. And (3) after cooling, transferring the reaction liquid into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain the triazatriindene thiophene bridged carbazole imide diene discotic liquid crystal (8) with the yield of 73%.
Synthesis of Trianilinodiene Compound of comparative example 1
Figure BDA0003168076510000131
Taking p-tribromoaniline (10g,20.75mmol) and ester diene boric acid (19.80g,62.24mmol) in a 500ml double-mouth round-bottom flask under the protection of nitrogen, adding 250ml of toluene as a solvent, installing a device, taking potassium carbonate (14.32g, 103.75mmol), completely dissolving the potassium carbonate with 30ml of water, adding the potassium carbonate into the round-bottom flask, and finally taking Pd (PPh)3)4(1.23g, 1.04mmol) in a flask, pumping off the air in the flask with an oil pump, introducing nitrogen, heating at constant temperature under reflux for 12 hours, and cooling. Transferring the reaction solution into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain the triphenylamine ester diene with the yield of 72%.
Measurement of Performance
1. Efficiency of photochemical crosslinking
In order to comparatively research the photochemical crosslinking performance of imide diene and ester diene, the invention utilizes OmniCure S2000 spot UV curing system equipment to select 100J/cm under different ultraviolet flux conditions2,200J/cm2,400J/cm2,600J/cm2,800J/cm2The crosslinking performance of the two types of photopolymerizable materials were compared. The UV light flux settings were selected from the S2000 application and UV exposure timing settings and OmniCure R2000 UV spot curing radiometer system. The energy of the ultraviolet light is chosen to be 365 nm. The material was dissolved in chlorobenzene to make 10mg/cm3And then the solution was spin-coated on the surface of the oxidized plasma-treated glass substrate at 2000rpm with an acceleration of 2000units for 30 seconds.
The comparative results are as follows:
ultraviolet luminous flux (365nm) Example 1 Example 2 Comparative example 1
100J/cm2 65％ 62％ 25％
200J/cm2 88％ 85％ 40％
400J/cm2 100％ 98％ 55％
600J/cm2 100％ 100％ 65％
800J/cm2 100％ 100％ 68％
The imide diene group of the invention has more stable performance than ester diene, and shows high-efficiency performance in the preparation and photocrosslinking processes.
2. Energy structure of organic compounds
The energy level of the organic material can be obtained by quantum calculation, for example, by Gaussian03W (Gaussian Inc.) using TD-DFT (including time density functional theory), and a specific simulation method can be found in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels were calculated according to the following calibration formula, and S1 and T1 were used directly.
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
Where HOMO (G) and LUMO (G) are direct calculations of Gaussian03W in Hartree. The results are shown in table 1:
TABLE 1
HOMO[eV] LUMO[eV] T1[eV] S1[eV]
Example 1 -5.46 -2.93 2.28 2.68
Example 2 -5.43 -2.99 2.23 2.70
Comparative example 1 -5.65 -2.63 1.75 3.13
3. Preparing and characterizing an OLED device:
ETL: a pyridine derivative; host is anthracene derivative;
the volume of the Dopan: a triarylamine derivative;
HIL: a triarylamine derivative;
HTL: the compound of example 1, the compound of example 2, the compound of comparative example 1.
Having an ITO/HIL (50nm)/HTL (35 nm)/Host: the preparation steps of the OLED device with 5% of Dopan (25nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode are as follows:
a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;
HIL (50nm), EML (25nm), ETL (28 nm): under high vacuum (1X 10)-6Mbar, mbar).
Htl (35 nm): the HTL layer was prepared by a solution method. The material was dissolved in chlorobenzene to make 10mg/cm3And then the solution was spin-coated on the surface of the oxidized plasma-treated glass substrate at 2000rpm with an acceleration of 2000units for 30 seconds. Selecting 800J/cm by OmniCure S2000 spot UV curing system equipment2And (4) carrying out crosslinking by ultraviolet light. The energy of the ultraviolet light is chosen to be 365 nm.
d. Cathode LiQ/Al (1nm/150nm) in high vacuum (1X 10)-6Millibar) hot evaporation;
e. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.
The current-voltage (J-V) characteristics of each OLED device were characterized by characterization equipment, while important parameters such as efficiency and lifetime were recorded. By detecting that the color coordinate of the blue light device prepared by using the compound of example 1 and the compound of example 2 as the hole transfer layer HTL is better than that of the comparative compound 1, such as the color coordinate X of the device prepared by using the compound of example 1 and the compound of example 2<0.15,Y<0.10; in addition, the luminous efficiency of the blue-ray device prepared by using the compound of example 1 and the compound of example 2 as HTL layers is in the range of 6-8cd/A, and the blue-ray device has more excellent luminous efficiency; the lifetime of blue devices prepared using the compound of example 1 and the compound of example 2 as the HTL layer is much better than that of comparative compound 1, e.g., T at 1000nits for devices prepared using the compound of example 1 and the compound of example 295Are all more than 2 times of the comparative examples. The detailed test results are shown in table 2.
TABLE 2
Efficiency (cd/A) Lifetime (T)951000nits) relative to comparative example 1 Color coordinates (CIE,1931)
Example 1 6.8 4.35 (0.13,0.07)
Example 2 6.4 3.85 (0.12,0.07)
Comparative example 1 3.5 1 (0.18,0.15)
The compound and the photoelectric device have large-plane conjugated triaza-trizin-triindene thiophene bridged carbazole groups, chemically stable high-efficiency photo-polymerization imide diene groups and disc-shaped liquid crystals arranged in an ordered molecular structure, and the combined advantages of the groups realize better carrier transmission and photoelectric response and better energy level matching, and improve the photoelectric performance and stability of the compound and the photoelectric device, thereby realizing higher efficiency, longer service life and more blue coordinates.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (8)

1. A photopolymerizable imide diene discotic liquid crystal of triazatriindane thiophene bridged carbazole of general formula (I):
Figure FDA0003168076500000011
wherein the content of the first and second substances,
R1identical or different in multiple occurrencesCan be H, D, F, -CN, -NO2、-CF3Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfone, substituted or unsubstituted alkyl of 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 60 carbon atoms, substituted or unsubstituted aromatic group of 6 to 60 carbon atoms, substituted or unsubstituted heterocyclic aromatic group of 3 to 60 carbon atoms, substituted or unsubstituted fused ring aromatic group of 7 to 60 carbon atoms, or fused ring aromatic group of 4 to 60 carbon atoms, or a ring-shaped aliphatic or aromatic ring system in which one or more groups may be bonded to each other and/or to the group to form a single ring or multiple rings;
R2the multiple occurrences, which may be the same or different, may be H, D, F, -CN, -NO2、-CF3Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfone, substituted or unsubstituted alkyl of 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 60 carbon atoms, substituted or unsubstituted aromatic group of 6 to 60 carbon atoms, substituted or unsubstituted heterocyclic aromatic group of 3 to 60 carbon atoms, substituted or unsubstituted fused ring aromatic group of 7 to 60 carbon atoms, or fused ring aromatic group of 4 to 60 carbon atoms, or a ring-shaped aliphatic or aromatic ring system in which one or more groups may be bonded to each other and/or to the group to form a single ring or multiple rings;
R3the multiple occurrences, which may be the same or different, may be H, D, F, -CN, -NO2、-CF3Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfone, substituted or unsubstituted alkyl of 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 60 carbon atoms, substituted or unsubstituted aromatic group of 6 to 60 carbon atoms, substituted or unsubstituted heterocyclic aromatic group of 3 to 60 carbon atoms, substituted or unsubstituted fused ring aromatic group of 7 to 60 carbon atoms, or fused ring aromatic group of 4 to 60 carbon atoms, or a ring-shaped aliphatic or aromatic ring system in which one or more groups may be bonded to each other and/or to the group to form a single ring or multiple rings.
2. A polymer comprising at least one repeating structural unit of the formula (I).
3. A mixture comprising at least one compound according to claim 1 or a polymer according to claim 2 and at least one further organic functional material selected from hole (also called hole) injection or transport materials (HIM/HTM), Hole Blocking Materials (HBM), electron injection or transport materials (EIM/ETM), Electron Blocking Materials (EBM), organic matrix materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermally-excited delayed fluorescence materials (TADF materials) and organic dyes.
4. A composition comprising at least one compound according to claim 1 or polymer according to claim 2 and at least one organic solvent.
5. An organic electronic device comprising an organic compound according to claim 1 or a high polymer according to claim 2.
6. The Organic electronic device according to claim 5, wherein the Organic electronic device is selected from the group consisting of Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (OFETs), Organic lasers, Organic spintronics, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes).
7. An organic electronic device according to claim 5, wherein the organic electronic device is an organic electroluminescent device comprising a hole transporting or injecting layer comprising a compound according to claim 1 or a polymer according to claim 2.
8. A method for preparing a functional layer comprising applying a compound of claim 1 by evaporation onto a substrate, or co-evaporating with at least one other organic functional material onto a substrate, or applying a composition of claim 4 by Printing or coating onto a substrate to form a functional layer, wherein the Printing or coating is selected from ink-jet Printing, jet Printing (Nozzle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexo Printing, rotary Printing, spray coating, brush coating or pad Printing, and slot die coating.
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