Compound containing TTF and pyridazine groups, preparation method thereof and organic photoelectric device

Abstract

The invention provides a compound containing TTF and pyridazine groups, a preparation method thereof and an organic photoelectric device, the compound has the following chemical structural formula: # imgabs0 #, R1 and R2 are respectively and independently selected from C1-C60 alkyl groups, and the compound has high thermal stability.

Description

Technical Field

[0001] The present application relates to the technical field, and in particular to a compound containing TTF and pyridazine groups, a preparation method thereof, and an organic optoelectronic device. Background Art

[0002] When a voltage is applied between two electrodes of an organic electroluminescent element (hereinafter referred to as an "organic EL element"), holes are injected from the anode and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light is emitted. At this time, the substances used for the organic layer can be divided into luminescent substances, hole injection substances, hole transport substances, electron transport substances, electron injection substances, etc. according to their functions.

[0003] The light-emitting layer forming materials of organic EL elements can be divided into blue, green and red light-emitting materials according to the light-emitting color. In addition, yellow and orange light-emitting materials are also used as light-emitting materials for presenting more natural colors. In addition, in order to increase the luminous efficiency by increasing the color purity and energy transfer, a host / dopant system can be used as a light-emitting material. Dopant substances can be divided into fluorescent dopants using organic substances and phosphorescent dopants using metal coordination compounds containing heavy atoms such as Ir and Pt. Since the development of such phosphorescent materials can theoretically improve the luminous efficiency by up to 4 times compared with fluorescence, not only phosphorescent dopants but also phosphorescent host materials have received attention.

[0004] So far, NPB, BCP, Alq3, etc. represented by the following chemical formula are widely known as hole injection layers, hole transport layers, hole blocking layers, and electron transport layers. Regarding light-emitting materials, anthracene derivatives have been reported as fluorescent dopants / host materials. In particular, as phosphorescent materials that have advantages in improving efficiency among light-emitting materials, metal coordination compounds containing Ir such as Firpic, Ir(ppy)3, (acac)Ir(btp)2, etc. have been used as blue, green, and red dopant materials.

[0005] However, the materials used in functional layers such as hole injection layer, hole transport layer, hole blocking layer, light emitting layer and electron transport layer have poor stability, which seriously affects the performance of the device. Therefore, it is urgent to prepare materials with high thermal stability as materials for functional layers. Summary of the invention

[0006] In view of this, the present application provides a compound containing TTF and pyridazine groups, a preparation method thereof, and an organic optoelectronic device to improve thermal stability.

[0007] The present application provides a compound containing TTF and pyridazine groups, having the following chemical structure:

[0008]

[0009] Here, R1 and R2 are each independently selected from C1 to C60 alkyl groups.

[0010] In some embodiments, R1 and R2 are each independently selected from C4 alkyl.

[0011] The present application also provides a method for preparing a compound containing TTF and a pyridazine group, comprising:

[0012] Providing a first compound and the second compound

[0013] Under the alkaline condition of DIPEA, the first compound and the second compound React to generate The R1 and the R2 are each independently selected from C1-C60 alkyl groups, and the R3 is selected from halogen elements.

[0014] In some embodiments, the first compound and the second compound The molar ratio is (0.7-1.2):(0.8-1.3).

[0015] In some embodiments, the first compound By the third compound And the fourth compound PO(R3)3 is reacted to form.

[0016] In some embodiments, the third compound The preparation includes:

[0017] Provide the first reactant

[0018] The first reactant Place in Hg(oAc)2 and CH2Cl2 to react and form the first intermediate product

[0019] The first intermediate product With the second reactant The reaction forms a second intermediate product

[0020] The second intermediate product React with the third reactant NH2NH2H2O to generate the third compound

[0021] In some embodiments, the first reactant By the fourth reactant and the fifth reactant To be formed.

[0022] In some embodiments, the fourth reactant is prepared

[0023] The sixth reactant Na2S 9H2O and the seventh reactant CS2 are dissolved in organic alcohol to react to form an intermediate

[0024] The intermediate With the eighth reactant Place in organic alcohol for reaction to form the fourth reactant The R5 and the R6 are selected from halogen elements.

[0025] In some embodiments, the second reactant By the sixth reactant and reacting with a seventh reactant AR4 to form, wherein A is R1 and R2, and R4 is selected from halogen elements.

[0026] The present application also provides an organic optoelectronic device, comprising a functional layer, wherein the material of the functional layer comprises the compound containing TTF and pyridazine groups as described above or the compound containing TTF and pyridazine groups prepared by the method for preparing the compound containing TTF and pyridazine groups as described above.

[0027] The present application provides a compound containing TTF and pyridazine groups, a preparation method thereof, and an organic optoelectronic device, having the following chemical structure:

[0028]

[0029] Wherein, R1 and R2 are each independently selected from C1-C60 alkyl groups for thermal stability. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application. In the absence of conflict, the following embodiments and their technical features can be combined with each other.

[0031] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present application, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined. In the description of the present application, the meaning of "several" is at least one, such as one, two, etc., unless otherwise clearly and specifically defined.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which this application belongs. The terms used herein are for the purpose of describing specific embodiments only and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more related listed items. The terms "connection", "electrical connection", and "electrical connection" used herein include any direct and indirect electrical or structural connection means. Therefore, if the text describes a first device coupled / connected / electrically connected to a second device, it means that the first device can be directly electrically / structurally connected to the second device, or indirectly electrically / structurally connected to the second device through other devices or connection means.

[0033] The present application provides a compound containing TTF and pyridazine groups, having the following chemical structure:

[0034] Wherein, R1 and R2 are independently selected from C1 to C60 alkyl groups. Specifically, R1 and R2 are independently selected from C1, C2, C4, C7, C10, C20, C30, C40, C50 or C60 alkyl groups, etc. The structural formula of the compound containing TTF and pyridazine groups can be

[0035]

[0036] wait.

[0037] In the present application, by introducing TTF and pyridazine groups into the compound, it has a higher thermodynamic stability, and the TTF group may also enhance the thermal stability of the compound by forming a stable complex; because the compound contains TTF group and pyridazine, when the two are combined together, the electron transfer or charge distribution change between the TTF group and the pyridazine can enhance the electron donating properties of the compound, that is, it has a higher electron mobility, the electrons are transmitted faster in the material, and the obstacles are less, which effectively improves the conductivity of the material, so that the current can pass more smoothly; the compound of the present application can be applied to identification fields such as environmental monitoring, pollution control or biomedical fields, and can accurately distinguish and bind organic cations (especially Hg2+), that is, highly selective recognition ability for organic cations. This means that it can accurately distinguish and bind Hg2+ in a complex chemical environment, while the binding ability to other ions or molecules is weak, and it can also be applied to the field of photoelectric luminescence.

[0038] In one embodiment, R1 and R2 are each independently an alkyl group selected from C4, and the structural formula of the compound containing TTF and pyridazine groups is

[0039]

[0040] The present application also provides a method for preparing a compound containing TTF and a pyridazine group, comprising:

[0041] Providing a first compound and the second compound

[0042] Under the alkaline condition of DIPEA, the first compound and the second compound React to generate R1 and R2 are independently selected from C1 to C60 alkyl groups, R3 is selected from halogen elements. Specifically, halogen elements include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), R1 and R2 are independently selected from C1, C2, C4, C7, C10, C20, C30, C40, C50 or C60 alkyl groups, etc., and the first compound can be

[0043] etc.; the structural formula of the compound containing TTF and pyridazine group formed can be

[0044]

[0045]

[0046] wait.

[0047] In the present application, the compound formed by this method contains a pyridazine group and a TTF group in the compound containing TTF and pyridazine groups, and the pyridazine group has a higher thermodynamic stability, and the TTF group may also enhance the thermal stability of the compound by forming a stable complex; because the compound contains a TTF group and a pyridazine, when the two are combined together, the electron donating properties of the compound can be enhanced, especially through the interaction of electron transfer or charge distribution changes between the TTF group and the pyridazine, that is, it has a higher electron mobility, and the speed of electron transmission in the material is faster and less obstructed, which effectively improves the conductive properties of the material and allows the current to pass more smoothly; the compound formed by the method of the present application can be applied to identification fields such as environmental monitoring, pollution control or biomedical fields, and can accurately distinguish and bind organic cations (especially Hg2+), that is, a highly selective recognition ability for organic cations. This means that it can accurately distinguish and bind Hg2+ in a complex chemical environment, while it has a weaker binding ability to other ions or molecules. In addition, it can also be used in the field of photoelectric luminescence. The chemical synthesis of this application adopts the "one-pot method" for synthesis, so that all reactants are in the same reaction container, through a series of continuous chemical reactions, directly generating the target product without the need for separation and purification in the intermediate steps. This method simplifies the synthesis process and improves efficiency.

[0048] In one embodiment, the first compound and the second compound The molar ratio of is (0.7-1.2): (0.8-1.3). Specifically, the first compound With the second compound The molar ratio can be 0.7:0.8, 0.8:0.8, 0.9:1.1 or 1.2:1.3, etc.

[0049] In one embodiment, the first compound By the third compound and the fourth compound PO(R3)3 to react to form. Specifically, the third compound can be The fourth compound may be POCl3.

[0050] In one embodiment, the third compound The preparation includes:

[0051] Provide the first reactant Then, the first reactant Place in Hg(oAc)2 and CH2Cl2 to react and form the first intermediate product Then, the first intermediate product With the second reactant The reaction is carried out to form a second intermediate product Then, the second intermediate product Reacts with the third reactant NH2NH2H2O to generate a third compound Specifically, the second reactant may be The second intermediate product can be The third compound generated can be

[0052] In one embodiment, the first reactant By the fourth reactant and the fifth reactant To be formed.

[0053] In one embodiment, the fourth reactant is prepared The steps include:

[0054] The sixth reactant Na2S 9H2O and the seventh reactant CS2 are dissolved in organic alcohol to react to form an intermediate Then, the intermediate With the eighth reactant Place in organic alcohol to react to form the fourth reactant R5 and R6 are selected from halogen elements. Specifically, the eighth reactant Can be Further, the halogen elements include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). The organic alcohol includes methanol, ethanol or propanol, etc.

[0055] In one embodiment, the second reactant By the sixth reactant and a seventh reactant AR4 to form, A is R1 and R2, R4 is selected from halogen elements. Further, the halogen elements include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). The seventh reactant can be C3H7Br, C4H9Br, C3H7Cl or C4H9I.

[0056] The sixth reactant is Na2S 9H2O, the seventh reactant is CS2, and the intermediate is The eighth reactant is The fourth reactant is The fifth reactant is The first reactant is The first intermediate product is The second reactant is The second intermediate product is The third reactant is NH2NH2H2O, and the third compound is The fourth compound is POCl3, and the first compound is The second compound is The compound containing TTF and pyridazine groups is formed as follows: Take this as an example. The chemical reaction equation is:

[0057]

[0058] Example

[0059] The sixth reactant Na2S 9H2O and the seventh reactant CS2 are dissolved in ethanol to react to form an intermediate Then, the intermediate With the eighth reactant Place in ethanol for reaction to form the fourth reactant Then, the fourth reactant With the fifth reactant To form the first reactant Then, the first reactant Place in Hg(oAc)2 and CH2Cl2 to react and form the first intermediate product Then, the first intermediate product With the second reactant The reaction forms a second intermediate product Then, the second intermediate product Reacts with the third reactant NH2NH2H2O to generate a third compound Then, the third compound React with the fourth compound ROCl3 to form the first compound The first compound and the second compound The reaction was carried out under alkaline conditions of DIPEA to form a compound containing TTF and pyridazine groups.

[0060]

[0061] The present application also provides an organic optoelectronic device, including a functional layer, wherein the material of the functional layer includes the compound containing TTF and pyridazine groups provided in the present application or the compound containing TTF and pyridazine groups prepared by the preparation method of the compound containing TTF and pyridazine groups provided in the present application. Specifically, the organic optoelectronic device includes a substrate, an anode, a functional layer and a cathode stacked in sequence, and the functional layer includes a hole injection layer (HIL), an electron injection layer (EIL), a hole transport layer (HTL), an electron transport layer (ETL), an electron blocking layer (EBL), a hole blocking layer (HBL) and a light-emitting layer (EML), wherein the material of at least one film layer of the hole injection layer (HIL), the electron injection layer (EIL), the hole transport layer (HTL), the electron transport layer (ETL), the electron blocking layer (EBL), the hole blocking layer (HBL) and the light-emitting layer (EML) contains the compound containing TTF and pyridazine groups provided in the present application.

[0062] The functional layer is prepared using the compound containing TTF and pyridazine groups provided in the present application. Since the compound containing TTF and pyridazine groups provided in the present application contains pyridazine groups and TTF groups, and the pyridazine groups have high thermodynamic stability, and the TTF groups may also enhance the thermal stability of the compound by forming a stable complex, the functional layer of the organic optoelectronic device can effectively resist the influence of the high temperature environment on the device, extend the service life of the device, maintain stable performance under long-term high temperature working conditions, and is not prone to performance degradation, luminous efficiency, and power consumption reduction; since the compound contains TTF groups and pyridazine, when the two are combined together, especially when applied to the electron transport layer, the electron transfer or charge distribution change interaction between the TTF group and the pyridazine can enhance the electron donating properties of the compound, that is, it has a higher electron mobility, the electrons are transmitted faster in the material, and are less obstructed, which effectively improves the conductive properties of the material, allows the current to pass more smoothly, and improves the performance of the device.

[0063] The above descriptions are merely embodiments of the present application and are not intended to limit the patent scope of the present application. Any equivalent structural or equivalent process transformations made using the contents of the present application specification, such as the mutual combination of technical features between the embodiments, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A compound containing TTF and pyridazine groups, characterized in that, It has the following chemical structure: Here, R1 and R2 are each independently selected from C1 to C60 alkyl groups.

2. The compound containing TTF and pyridazine groups according to claim 1, characterized in that R1 and R2 are each independently selected from C4 alkyl groups.

3. A method for preparing a compound containing TTF and pyridazine groups, characterized in that: include: Providing a first compound and the second compound Under the alkaline condition of DIPEA, the first compound and the second compound React to generate The R1 and the R2 are each independently selected from C1-C60 alkyl groups, and the R3 is selected from halogen elements.

4. The method for preparing a compound containing TTF and pyridazine groups according to claim 3, characterized in that: The first compound and the second compound The molar ratio is (0.7-1.2):(0.8-1.3).

5. The method for preparing a compound containing TTF and pyridazine groups according to claim 3, characterized in that: The first compound By the third compound And the fourth compound PO(R3)3 is reacted to form.

6. The method for preparing a compound containing TTF and pyridazine groups according to claim 5, characterized in that: The third compound The preparation includes: Provide the first reactant The first reactant Place in Hg(oAc)2 and CH2Cl2 to react and form the first intermediate product The first intermediate product With the second reactant The reaction is carried out to form a second intermediate product The second intermediate product React with the third reactant NH2NH2H2O to generate the third compound 7. The method for preparing a compound containing TTF and pyridazine groups according to claim 6, characterized in that: The first reactant By the fourth reactant and the fifth reactant To be formed.

8. The method for preparing a compound containing TTF and pyridazine groups according to claim 7, characterized in that: Preparation of the fourth reactant The sixth reactant Na2S 9H2O and the seventh reactant CS2 are dissolved in organic alcohol to react to form an intermediate The intermediate With the eighth reactant Place in organic alcohol for reaction to form the fourth reactant The R5 and the R6 are selected from halogen elements.

9. The method for preparing a compound containing TTF and pyridazine groups according to claim 6, characterized in that: The second reactant By the sixth reactant and reacting with a seventh reactant AR4 to form, wherein A is R1 and R2, and R4 is selected from halogen elements.

10. An organic optoelectronic device, characterized in that: It comprises a functional layer, wherein the material of the functional layer comprises the compound containing TTF and pyridazine groups as claimed in any one of claims 1-2 or the compound containing TTF and pyridazine groups prepared by the preparation method of the compound containing TTF and pyridazine groups as claimed in any one of claims 3-9.

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