Quinoline formaldehyde palladium complex as well as preparation method and application thereof

Abstract

The invention discloses a quinoline formaldehyde palladium complex as well as a preparation method and application thereof, the structural formula of the quinoline formaldehyde palladium complex is shown as a formula (I): # imgabs0 # formula (I), wherein R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen or formaldehyde; the quinoline formaldehyde palladium complex provided by the invention can be catalytically polymerized at a high temperature to prepare a long ether chain thiophene copolymer with high molecular weight and high regularity, and has wide application prospects in the fields of solar cells, organic transistors, electrochromic devices, chemical sensors, electromagnetic shielding materials and the like.

Description

Technical Field

[0001] The invention relates to the technical field of quinoline carboxaldehyde palladium complexes, and in particular to a quinoline carboxaldehyde palladium complex and a preparation method and application thereof. Background Art

[0002] Perovskite solar cells are a type of solar cell with great development prospects that has emerged in recent years. They have the advantages of high photoelectric conversion efficiency, simple production, and low cost. Photoelectric conversion efficiency is one of the important performance indicators for measuring the quality of perovskite solar cells. At present, there are two main technical means to improve the photoelectric conversion efficiency of perovskite solar cells. One is to optimize the interface performance by optimizing the structure or regulating the morphology of each layer of the perovskite cell; the other is to change the material composition of the perovskite cell and develop hole transport layer, perovskite absorption layer or electron transport layer materials with better performance.

[0003] The molecular chain of thiophene homopolymer or thiophene copolymer contains a π-π conjugated system, which exhibits unique optical, electrical and electrochemical properties. In addition, thiophene homopolymer or thiophene copolymer has the advantages of excellent charge carrier mobility, high absorption coefficient, good near-infrared absorption ability, etc., and is widely used in hole transport layers.

[0004] Poly (3-hexylthiophene) is one of the most commonly used polymer hole transport materials. However, the efficiency of perovskite solar devices prepared using P3HT alone as a hole transport layer is not ideal. The main reason is that P3HT has poor physical contact with the perovskite interface, which causes serious recombination of carriers, resulting in significant voltage and current losses, thereby affecting the energy conversion efficiency of perovskite solar cells. The inventors found in the experimental process that copolymerizing long ether chain thiophene with P3HT can improve the problem of poor physical contact between P3HT and the perovskite interface. But so far, there are few existing technical records of catalysts that can be used to prepare copolymerization of long ether chain thiophene and P3HT. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects and shortcomings of the prior art and provide a quinoline formaldehyde palladium complex. The quinoline formaldehyde palladium complex can be catalytically polymerized at high temperature to obtain a high-molecular-weight, high-regularity long-ether-chain thiophene copolymer, which has broad application prospects in the fields of solar cells, organic transistors, electrochromic devices, chemical sensors, electromagnetic shielding materials, etc.

[0006] The object of the present invention is to provide a quinolinecarboxaldehyde palladium complex, the structural formula of the quinolinecarboxaldehyde palladium complex is shown in formula (I):

[0007] Formula (I) Among them, R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 are independently selected from hydrogen or carboxaldehyde.

[0008] Another object of the present invention is to provide a method for preparing a quinolinecarboxaldehyde palladium complex, comprising the steps of: Ligand With PdCl 2 Reaction to obtain the quinoline formaldehyde palladium complex.

[0009] In some embodiments of the present invention, the ligand and PdCl 2 The molar ratio is 1:0.51~0.55.

[0010] In some embodiments of the present invention, the reaction temperature is 70-90° C. and the reaction time is 10-50 min.

[0011] Another object of the present invention is to provide the use of the quinolinecarboxaldehyde palladium complex or the quinolinecarboxaldehyde palladium complex prepared by the preparation method of the quinolinecarboxaldehyde palladium complex in the preparation of long ether chain thiophene copolymers.

[0012] In some embodiments of the present invention, the structure of the long ether chain thiophene copolymer is shown in formula (II):

[0013] Formula (II) Wherein, the number average molecular weight of the long ether chain thiophene copolymer is 7.98~10.4KDa.

[0014] In some embodiments of the present invention, the molar percentage of the 3-(2-butoxyethyl)thiophene segment in the long ether chain thiophene copolymer segment is 5.3% to 15.1%.

[0015] In some embodiments of the present invention, the molar percentage of the 3-(2-butoxyethyl)thiophene segment in the long ether chain thiophene copolymer segment is 12.4% to 15.1%.

[0016] In some embodiments of the present invention, the HT value of the long ether chain thiophene copolymer is ≥90%, and the PDI is ≥2.5.

[0017] In some embodiments of the present invention, the long ether chain thiophene copolymer is a random copolymer.

[0018] Another object of the present invention is to provide a method for preparing a long ether chain thiophene copolymer, comprising the following steps: Under the catalysis of the quinoline carboxaldehyde palladium complex shown in formula (I), 2-bromo-3-(2-butoxyethyl)thiophene and 2-bromo-3-hexylthiophene react to obtain the long ether chain thiophene copolymer; The structural formula of the quinoline carboxaldehyde palladium complex represented by formula (I) is as follows:

[0019] Formula (I) Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are independently selected from hydrogen or carboxaldehyde.

[0020] In some embodiments of the present invention, the molar ratio of 2-bromo-3-(2-butoxyethyl)thiophene to 2-bromo-3-hexylthiophene is 1-5:15-19.

[0021] In some embodiments of the present invention, the ratio of the total mole of 2-bromo-3-(2-butoxyethyl)thiophene and 2-bromo-3-hexylthiophene to the mole of quinolinecarboxaldehyde palladium complex is 1:0.001-0.01.

[0022] In some embodiments of the present invention, the reaction temperature is 80-120° C. and the reaction time is 12-36 hours.

[0023] In some embodiments of the present invention, the reaction further contains an inorganic base, an organic acid and a solvent.

[0024] In some embodiments of the present invention, the inorganic base includes at least one of potassium carbonate and sodium carbonate.

[0025] In some embodiments of the present invention, the organic acid includes at least one of pivalic acid and caproic acid.

[0026] In some embodiments of the present invention, the solvent includes N,N-dimethylacetamide.

[0027] In some embodiments of the present invention, the ratio of the total mole of 2-bromo-3-(2-butoxyethyl)thiophene and 2-bromo-3-hexylthiophene to the mole of the inorganic base is 1-1.5:1-1.5.

[0028] In some embodiments of the present invention, the ratio of the total mole of 2-bromo-3-(2-butoxyethyl)thiophene and 2-bromo-3-hexylthiophene to the mole of the organic acid is 2.5-4.5:1.

[0029] In some embodiments of the present invention, after the reaction is completed, a purification step is further included.

[0030] Compared with the prior art, the present invention has the following beneficial effects: The quinoline formaldehyde palladium complex provided by the present invention can be used to prepare long ether chain thiophene copolymers at high temperature. The prepared long ether chain thiophene copolymers have the advantages of high molecular weight and high regularity, and have obvious economic benefits. They have broad application prospects in the fields of solar cells, organic transistors, electrochromic devices, chemical sensors, electromagnetic shielding materials, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the H NMR spectrum of the quinolinecarboxaldehyde palladium complex C1 provided in Example 1. DETAILED DESCRIPTION

[0032] The following will clearly and completely describe the concept of the present invention and the technical effects produced in combination with the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by technicians in this field without creative work are all within the scope of protection of the present invention. The test methods used in the embodiments are all conventional methods unless otherwise specified; the materials, reagents, etc. used, unless otherwise specified, can all be reagents and materials obtained from commercial channels.

[0033] Quinoline carboxaldehyde palladium complex is prepared by the following reaction route:

[0034] In the following examples, the content of 3-(2-butoxyethyl)thiophene segments in the long ether chain thiophene copolymer was determined by nuclear magnetic resonance, the long ether chain thiophene copolymer was dissolved in deuterated chloroform, TMS was used as an internal standard, and the measurement temperature was 25°C. The molecular weight or degree of polymerization of the long ether chain thiophene copolymer was determined by gel permeation chromatography (GPC) with THF mobile phase. Among them, HT and HT values ​​represent isotacticity, and PDI represents molecular weight distribution index; The structural formula of 2-bromo-3-(2-butoxyethyl)thiophene is shown below: .

[0035] Example 1

[0036] This embodiment provides a quinoline carboxaldehyde palladium complex C1, and its synthesis method is as follows: 8-Quinolinecarboxaldehyde (1 mmol), PdCl 2(0.51mmol) and dimethylacetamide (3ml) were added into a 10ml single-mouth bottle respectively, and the reaction was carried out at 80℃ for 0.5h. After the reaction was completed, the mixture was cooled to room temperature and methanol was added for precipitation to obtain a yellow solid compound C1 with a yield of 86%.

[0037] Example 2

[0038] This embodiment provides a quinoline carboxaldehyde palladium complex C2, and its synthesis method is as follows: 7-Quinolinecarboxaldehyde (1 mmol), PdCl 2 (0.51mmol) and dimethylacetamide (3ml) were added into a 10ml single-mouth bottle respectively, and the reaction was carried out at 80℃ for 0.5h. After the reaction was completed, the mixture was cooled to room temperature and methanol was added for precipitation to obtain a yellow solid compound C2 with a yield of 83%.

[0039] Example 3

[0040] This embodiment provides a quinoline carboxaldehyde palladium complex C3, and its synthesis method is as follows: 6-Quinolinecarboxaldehyde (1 mmol), PdCl 2 (0.51mmol) and dimethylacetamide (3ml) were added into a 10ml single-mouth bottle respectively, and the reaction was carried out at 80℃ for 0.5h. After the reaction was completed, the mixture was cooled to room temperature and methanol was added for precipitation to obtain a yellow solid compound C3 with a yield of 80%.

[0041] Example 4

[0042] This embodiment provides a quinoline carboxaldehyde palladium complex C4, and its synthesis method is as follows: 5-Quinolinecarboxaldehyde (1 mmol), PdCl 2 (0.51mmol) and dimethylacetamide (3ml) were added into a 10ml single-mouth bottle respectively, and the reaction was carried out at 80℃ for 0.5h. After the reaction was completed, the mixture was cooled to room temperature and methanol was added for precipitation to obtain a yellow solid compound C4 with a yield of 84%.

[0043] Example 5

[0044] This embodiment provides a quinoline carboxaldehyde palladium complex C5, and its synthesis method is as follows: 4-Quinolinecarboxaldehyde (1 mmol), PdCl 2 (0.51mmol) and dimethylacetamide (3ml) were added into a 10ml single-mouth bottle respectively, and the reaction was carried out at 80℃ for 0.5h. After the reaction was completed, the mixture was cooled to room temperature and methanol was added for precipitation to obtain a yellow solid compound C5 with a yield of 87%.

[0045] Example 6

[0046] This embodiment provides a quinoline carboxaldehyde palladium complex C6, and its synthesis method is as follows: 3-Quinolinecarboxaldehyde (1 mmol), PdCl 2 (0.51mmol) and dimethylacetamide (3ml) were added into a 10ml single-mouth bottle respectively, and the reaction was carried out at 80℃ for 0.5h. After the reaction was completed, the mixture was cooled to room temperature and methanol was added for precipitation to obtain a yellow solid compound C6 with a yield of 85%.

[0047] Example 7

[0048] This embodiment provides a quinoline carboxaldehyde palladium complex C7, and its synthesis method is as follows: 2-Quinolinecarboxaldehyde (1 mmol), PdCl 2 (0.51mmol) and dimethylacetamide (3ml) were added into a 10ml single-mouth bottle respectively, and the reaction was carried out at 80℃ for 0.5h. After the reaction was completed, the mixture was cooled to room temperature and methanol was added for precipitation to obtain a yellow solid compound C7 with a yield of 86%.

[0049] Example 8

[0050] This embodiment provides a long ether chain thiophene copolymer L1, and the synthesis method thereof is as follows: Under nitrogen atmosphere, 2-bromo-3-(2-butoxyethyl)thiophene (0.03mmol), 2-bromo-3-hexylthiophene (0.47mmol), potassium carbonate (0.75mmol), quinoline carboxaldehyde palladium complex C1 (0.25mmol%), pivalic acid (0.15mmol), dimethylacetamide (4mL) were reacted at 100°C for 24h, and precipitated in methanol to obtain a long ether chain thiophene copolymer L1 with a yield of 76%, an HT value of 92%, a PDI of 2.58, a number average molecular weight Mn of 10.4KDa, and a molar percentage of 3-(2-butoxyethyl)thiophene segments in the long ether chain thiophene copolymer segments of 5.3%, that is, a copolymerization degree of 5.3mmol; the structures of the quinoline carboxaldehyde palladium complex C1 and the random long ether chain thiophene copolymer L1 are shown below:

[0051] Among them, x=5.3mmol%, y=94.7mmol%.

[0052] Example 9

[0053] This embodiment provides a long ether chain thiophene copolymer L2, and its synthesis method is as follows: Under nitrogen atmosphere, 2-bromo-3-(2-butoxyethyl)thiophene (0.08mmol), 2-bromo-3-hexylthiophene (0.492mmol), potassium carbonate (0.75mmol), quinoline carboxaldehyde palladium complex C2 (0.25mmol%), pivalic acid (0.15mmol), dimethylacetamide (4mL) were reacted at 100°C for 24h, and precipitated in methanol to obtain a long ether chain thiophene copolymer L2 with a yield of 72%, a HT value of 90%, a PDI of 2.72, a number average molecular weight Mn of 7.98KDa, and a molar percentage of 3-(2-acetoxymethyl)thiophene segments in the long ether chain thiophene copolymer segments of 15.1%, that is, a copolymerization degree of 15.1mmol; the structures of the quinoline carboxaldehyde palladium complex C2 and the long ether chain thiophene copolymer L2 are shown below:

[0054] Among them, x=15.1mmol%, y=84.9mmol%.

[0055] Example 10

[0056] This embodiment provides a long ether chain thiophene copolymer L3, and its synthesis method is as follows: Under nitrogen atmosphere, 2-bromo-3-(2-butoxyethyl)thiophene (0.075mmol), 2-bromo-3-hexylthiophene (0.425mmol), potassium carbonate (0.75mmol), quinoline carboxaldehyde palladium complex C3 (0.25mmol%), pivalic acid (0.15mmol), dimethylacetamide (4mL) were reacted at 100°C for 24h, and precipitated in methanol to obtain a long ether chain thiophene copolymer L3 with a yield of 70%, an HT value of 93%, a PDI of 2.69, a number average molecular weight Mn of 8.34KDa, and a molar percentage of 3-(2-acetoxyethyl)thiophene segments in the long ether chain thiophene copolymer segments of 12.4%, that is, a copolymerization degree of 12.4mmol; the structures of the quinoline carboxaldehyde palladium complex C3 and the long ether chain thiophene copolymer L3 are as follows:

[0057] Among them, x=12.4mmol%, y=87.6mmol%.

[0058] Embodiment 11

[0059] This embodiment provides a long ether chain thiophene copolymer L4, and its synthesis method is as follows: Under nitrogen atmosphere, 2-bromo-3-(2-butoxyethyl)thiophene (0.04mmol), 2-bromo-3-hexylthiophene (0.46mmol), potassium carbonate (0.75mmol), quinoline carboxaldehyde palladium complex C4 (0.25mmol%), pivalic acid (0.15mmol), dimethylacetamide (4mL) were reacted at 100°C for 24h, and precipitated in methanol to obtain a long ether chain thiophene copolymer L4 with a yield of 80%, a HT value of 92%, a PDI of 2.81, a number average molecular weight Mn of 9.8KDa, and a molar percentage of 3-(2-acetoxyethyl)thiophene segments in the long ether chain thiophene copolymer segments of 6.7%, that is, a copolymerization degree of 6.7mmol; the structures of the quinoline carboxaldehyde palladium complex C4 and the long ether chain thiophene copolymer L4 are shown below:

[0060] Among them, x=6.7mmol%, y=93.3mmol%.

[0061] Example 12

[0062] This embodiment provides a long ether chain thiophene copolymer L5, and its synthesis method is as follows: Under nitrogen atmosphere, 2-bromo-3-(2-butoxyethyl)thiophene (0.045mmol), 2-bromo-3-hexylthiophene (0.455mmol), potassium carbonate (0.75mmol), quinoline carboxaldehyde palladium complex C5 (0.25mmol%), pivalic acid (0.15mmol), dimethylacetamide (4mL) were reacted at 100°C for 24h, and precipitated in methanol to obtain a long ether chain thiophene copolymer L5 with a yield of 77%, an HT value of 95%, a PDI of 2.76, a number average molecular weight Mn of 9.6KDa, and a molar percentage of 3-(2-acetoxyethyl)thiophene segments in the long ether chain thiophene copolymer segments of 7.2%, that is, a copolymerization degree of 7.2mmol; the structures of the quinoline carboxaldehyde palladium complex C5 and the long ether chain thiophene copolymer L5 are shown as follows:

[0063] Among them, x=7.2mmol%, y=92.8mmol%.

[0064] Embodiment 13

[0065] This embodiment provides a long ether chain thiophene copolymer L6, and its synthesis method is as follows: Under nitrogen atmosphere, 2-bromo-3-(2-butoxyethyl)thiophene (0.045mmol), 2-bromo-3-hexylthiophene (0.455mmol), potassium carbonate (0.75mmol), quinoline carboxaldehyde palladium complex C6 (0.25mmol%), pivalic acid (0.15mmol), dimethylacetamide (4mL) were reacted at 100°C for 24h, and precipitated in methanol to obtain a long ether chain thiophene copolymer L6 with a yield of 74%, a HT value of 94%, a PDI of 2.62, a number average molecular weight Mn of 9.3KDa, and a molar percentage of 3-(2-acetoxyethyl)thiophene segments in the long ether chain thiophene copolymer segments of 7.9%, that is, a copolymerization degree of 7.9mmol; the structures of the quinoline carboxaldehyde palladium complex C6 and the long ether chain thiophene copolymer L6 are shown below:

[0066] Among them, x=7.9mmol%, y=92.1mmol%.

[0067] Embodiment 14

[0068] This embodiment provides a long ether chain thiophene copolymer L7, and its synthesis method is as follows: Under nitrogen atmosphere, 2-bromo-3-(2-butoxyethyl)thiophene (0.055mmol), 2-bromo-3-hexylthiophene (0.445mmol), potassium carbonate (0.75mmol), quinoline carboxaldehyde palladium complex C7 (0.25mmol%), pivalic acid (0.15mmol), dimethylacetamide (4mL) were reacted at 100°C for 24h, and precipitated in methanol to obtain a long ether chain thiophene copolymer L7 with a yield of 70%, an HT value of 921%, a PDI of 2.59, a number average molecular weight Mn of 9.1KDa, and a molar percentage of 3-(2-acetoxyethyl)thiophene segments in the long ether chain thiophene copolymer segments of 8.4%, that is, a copolymerization degree of 8.4mmol; the structures of the quinoline carboxaldehyde palladium complex C7 and the long ether chain thiophene copolymer L7 are shown below:

[0069] Among them, x=8.4mmol%, y=91.6mmol%.

[0070] It can be seen from Examples 8 to 14 that the long ether chain thiophene copolymer of the present invention has a random structure and has the characteristics of high regularity and high molecular weight.

[0071] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A quinolinecarboxaldehyde palladium complex, characterized in that The structural formula of the quinoline formaldehyde palladium complex is shown in formula (I): Formula (I) Wherein, R1, R2, R3, R4, R5, R6, and R7 are independently selected from hydrogen or formaldehyde.

2. The method for preparing the quinolinecarboxaldehyde palladium complex according to claim 1, wherein The steps include: Ligand The quinoline formaldehyde palladium complex is obtained by reacting with PdCl2.

3. The preparation method of quinolinecarboxaldehyde palladium complex according to claim 2, characterized in that, The molar ratio of the ligand to PdCl2 is 1:0.51-0.

55.

4. The preparation method of quinolinecarboxaldehyde palladium complex according to claim 2, characterized in that The reaction temperature is 70-90°C and the reaction time is 10-50 minutes.

5. Use of the quinolinecarboxaldehyde palladium complex according to claim 1 or the quinolinecarboxaldehyde palladium complex prepared by the preparation method of the quinolinecarboxaldehyde palladium complex according to any one of claims 2 to 4 in the preparation of long ether chain thiophene copolymers.

6. The use according to claim 5, characterized in that: The structure of the long ether chain thiophene copolymer is shown in formula (II): Formula (II) Wherein, the number average molecular weight of the long ether chain thiophene copolymer is 7.98~10.4KDa.

7. The use according to claim 5, characterized in that: The molar percentage of the 3-(2-butoxyethyl)thiophene chain segment to the long ether chain thiophene copolymer chain segment is 5.3% to 15.1%.

8. The use according to claim 5, characterized in that: The molar percentage of the 3-(2-butoxyethyl)thiophene chain segment to the long ether chain thiophene copolymer chain segment is 12.4% to 15.1%.

9. The use according to claim 5, characterized in that: The long ether chain thiophene copolymer has an HT value of ≥90% and a PDI of ≥2.

5.

10. The use according to claim 5, characterized in that: The long ether chain thiophene copolymer is a random copolymer.

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