Photoresponsive mononuclear nickel / palladium complexes for the preparation of ultrahigh molecular weight polyethylene, and methods of making and using the same

Abstract

The application provides a kind of preparation of ultra-high molecular weight polyethylene photoresponsive type mononuclear nickel / palladium complex and its preparation method and application, structural formula is as shown below:Photoresponsive type nickel / palladium complex provided by the application has rigid stilbene skeleton, and is converted from trans configuration (E) to cis configuration (Z) under 365nm ultraviolet light irradiation, and is converted from cis configuration (Z) to trans configuration (E) under 405nm ultraviolet light irradiation.Therefore, the proportion of E formula configuration and Z formula configuration in photoresponsive type nickel complex can be accurately regulated by ultraviolet light irradiation, the reaction rate of two different sites in olefin polymerization process is adjusted by using the photoresponsive type nickel complex as catalyst, and then the molecular weight and the insertion rate of polar monomer of polyolefin material are regulated.The obtained ultra-high molecular weight polyethylene has a molecular weight distribution of 1.60-2.57, a molecular weight of 632-1184*10 4 g·mol ‑1 , and the catalyst has ultra-high catalytic activity, can produce high-performance polyethylene, can greatly reduce the production cost of catalyst, and has great industrial application potential.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a photoresponsive mononuclear nickel / palladium complex for preparing ultra-high molecular weight polyethylene, its preparation method, and its application. Background Technology

[0002] The iterative updates to olefin polymerization catalysts have injected more diverse product types and greater practical value into polyolefin materials. Polyolefins encompass five major categories: high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), and polypropylene (PP). Among them, UHMWPE possesses a series of properties such as chemical corrosion resistance, wear resistance, impact resistance, and self-lubrication, and is currently widely used in many industries such as biomedicine, military equipment, and membrane batteries.

[0003] Currently, 70% of global UHMWPE production still uses supported Zn catalysts in its industrial production. However, these catalysts often produce polymers with extremely low branching (less than 1 / 100,000) and a wide molecular weight distribution (approximately 5–20), making them extremely difficult to process using traditional techniques. As for metallocene catalysts, not only are they expensive co-catalysts, but metallocene complexes suitable for synthesizing ultra-high molecular weight polyethylene are also scarce.

[0004] Therefore, researchers have focused their research on non-agronomical post-transition catalysts. Through the careful design and synthesis of ligands, precise control over the polymer structure can be achieved, thereby obtaining ultra-high molecular weight polyethylene with a narrow molecular weight distribution. In recent years, the research groups of Jian Zhongbao, Dai Shengyu, and Sun Wenhua have successfully designed catalysts that can be used to prepare ultra-high molecular weight polyethylene (Mw = 126–467 × 10⁻⁶). 4 g·mol -1 ) (J. Catal., 2020, 390, 30, CN111548285A; Organometallics, 2022, 41, 124, CN114349658A; Polym. Chem., 2023, 14, 183; Polymer, 2024, 293, 126690).

[0005] Besides utilizing the electronic and steric effects of ligands in catalysts as discussed above, secondary coordination effects and weak intermolecular interactions are also used to implement internal control strategies for the catalyst itself. However, this approach has led to a continuous increase in the complexity of synthesizing novel catalysts in recent years, and the synthesized catalysts often exhibit only a single catalytic performance. In addition to internal control methods, introducing stimulus-responsive structural units into the framework of polymerization catalysts is also a feasible approach. That is, during the polymerization reaction, external stimuli (such as redox reactions, electrochemical processes, mechanochemical control, acid / base environments, and light) can induce the originally single catalyst precursor to derive one or more catalytically active species. Given the differences in polymerization activity exhibited by different catalytically active centers, this allows for effective control of the polymerization process.

[0006] Among various external stimuli, light is an ideal source due to its high versatility, environmental friendliness, and ease of operation. Therefore, using light to regulate polymerization processes and polymer microstructures is of great research value and appeal. In recent years, some researchers have attempted to introduce azobenzene functional groups into catalyst systems, leveraging the photoinduced isomerization properties of these groups to regulate the microstructure of polyolefin materials (Macromolecules, 2019, 52, 5646; Angew. Chem. Int. Ed. 2021, 60, 22195; Chin. J. Chem. 2022, 40, 2919; Chin. Chem. Lett., 2024, 35, 109534). However, due to the relatively high repulsion energy between the two phenyl groups in azobenzene compounds, its cis structure is relatively unstable and gradually transforms into a trans structure even at room temperature. This makes it difficult to precisely control the fine structure of polyethylene materials at high temperatures by adjusting the cis-trans ratio of catalysts using azobenzene functional groups as photoswitches. To address this challenge, in 2024, Chen Changle's research group and Jiang Hui's research group (Sci. China Chem. 2024, https: / / doi.org / 10.1007 / s11426-024-2201-6 This study innovatively introduced a rigid diphenylethylene skeleton into the catalyst system, successfully controlling the polymerization process and obtaining polymers with different properties by leveraging the photocatalytic effect. However, unfortunately, few of the obtained polymers were copolymers with enols and olefins. The non-polar nature of polyethylene, while providing chemical stability, also limits its wider industrial applications. Direct coordination copolymerization of ethylene with polar monomers does not require stringent experimental conditions, but has so far achieved only limited success.

[0007] In summary, given the instability of the cis structure in existing catalysts using azobenzene functional groups as photoswitches, which makes it difficult to control the fine structure of polyethylene materials at high temperatures by adjusting the cis-trans ratio, and the urgent need to improve catalyst activity to produce high-performance high-end polyolefins, the development of a class of photoresponsive catalysts for the catalytic synthesis of functionalized high-end polyethylene has become a top priority. Summary of the Invention

[0008] To address the issue of unstable cis-structure catalysts using azobenzene functional groups as photoswitches in existing technologies, and the urgent need to improve catalyst activity for producing high-performance high-end polyolefins, this invention provides a temperature-insensitive rigid diphenylethylene photoresponsive mononuclear imine nickel / palladium complex. This photoresponsive nickel complex is stable at 120°C and undergoes configurational inversions under two different wavelengths of ultraviolet light irradiation: a transformation from trans (E) to cis (Z) configuration under 365 nm ultraviolet light irradiation, and a transformation from cis (Z) to trans (E) configuration under 405 nm ultraviolet light irradiation. Therefore, the ratio between the E and Z configurations of the photoresponsive nickel complex can be precisely controlled using ultraviolet light irradiation. When this photoresponsive nickel complex is used as a catalyst, the reaction rate in the olefin polymerization process can be adjusted, thereby achieving effective control over the molecular weight and polar monomer insertion rate of the polyolefin material.

[0009] Furthermore, the complex of this application exhibits high catalytic activity in ethylene polymerization and good thermal stability; the resulting ultra-high molecular weight polyethylene has a molecular weight distribution of 1.60–2.57 and a molecular weight of 632–1184 × 10⁻⁶. 4 g·mol -1 It also has good physical and mechanical properties, with an elastic recovery rate of up to 92%.

[0010] The technical solution provided by this invention is as follows:

[0011] In a first aspect, the present invention provides imine nickel / palladium complexes having the chemical structures shown in formulas E-(I), Z-(I), E-(II), and Z-(II):

[0012]

[0013] Where R 1 R is one of hydrogen, cyano, OCH2CH2OCH3, or substituted phenyl. 2 It is one of hydrogen, halogen, or alkoxy; M is one of the metals Ni or Pd.

[0014] Preferably, the α-diimine nickel / palladium complex with the chemical structure shown in formula E-(I) includes at least one of E-(I)-1 to E-(I)-5, the pyridineimine nickel / palladium complex with the chemical structure shown in formula E-(II) includes at least one of E-(II)-1 to E-(II)-3, the α-diimine nickel / palladium complex with the chemical structure shown in formula Z-(I) includes at least one of Z-(I)-1 to Z-(I)-5, and the pyridineimine nickel / palladium complex with the chemical structure shown in formula Z-(II) includes at least one of Z-(II)-1 to Z-(II)-3.

[0015]

[0016] In a second aspect, the present invention provides a method for synthesizing α-diimine nickel / palladium complexes having the chemical structures shown in formulas E-(I) and Z-(I), comprising:

[0017] Compound E / Z-1 and compound 5 undergo a Suzuki coupling reaction at 80–120 °C under the catalysis of a second catalyst to generate the aniline compound shown in formula E / Z-2. Compound E / Z-2 and compound 6 undergo a Suzuki coupling reaction at 80–120 °C under the catalysis of a second catalyst to generate the aniline compound shown in formula E / Z-3. Compound 7 and the aniline compound shown in formula E / Z-3 undergo a condensation reaction at 80–120 °C under the catalysis of a third catalyst to generate the α-diimine compound shown in formula E / Z-4.

[0018] The α-diimine compound shown in formula E / Z-4 is reacted with (DME)NiBr2 or (COD)PdMeCl at 0–45 °C to generate α-diimine nickel / palladium complexes having the chemical structures shown in formulas E-(I) and Z-(I).

[0019]

[0020]

[0021] R 1 R is one of hydrogen, cyano, OCH2CH2OCH3, or substituted phenyl. 2 It is one of hydrogen, halogen, or alkoxy.

[0022] The second catalyst is tetra(triphenylphosphine)palladium or 1,1'-bis(diphenylphosphine)ferrocene palladium(II);

[0023] The third catalyst is zinc dichloride or p-toluenesulfonic acid.

[0024] In the method for synthesizing the bisimine compound having the chemical structure shown in Formula E / Z-3 provided by the present invention, the molar ratio of Formula E / Z-1 to compound 5 is (1-2):1; the molar ratio of Formula E / Z-2 to compound 6 (2,6-diisopropyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)aniline) is (1-2):1; and the molar ratio of compound 7 to formula E / Z-3 is (1-2):1.

[0025] Thirdly, the present invention provides a method for synthesizing pyridineimine nickel / palladium complexes having the chemical structures shown in formulas E-(II) and Z-(II), comprising:

[0026] Compound 9 and formula E / Z-3 were subjected to a condensation reaction at 80–120 °C under the catalysis of a fourth catalyst to generate the pyridineimine compound shown in formula E / Z-8;

[0027] The pyridineimine compound shown in formula E / Z-8 is reacted with (DME)NiBr2 or (COD)PdMeCl at 0–45 °C to generate pyridineimine nickel / palladium complexes having the chemical structures shown in formulas E-(II) and Z-(II).

[0028] The reaction route is as follows:

[0029]

[0030] Among them, R 1 It is one of hydrogen, cyano, OCH2CH2OCH3, or substituted phenyl.

[0031] The fourth catalyst is zinc dichloride or p-toluenesulfonic acid.

[0032] In the method for synthesizing pyridineimine compounds having the chemical structure shown in Formula E / Z-8 provided by the present invention, the molar ratio of compound 9 to formula E / Z-3 is (1-2):1.

[0033] In the method for synthesizing α-diimine nickel / palladium complexes having the formula E-(I) / Z-(I) and the chemical structure shown in this invention, the reaction time of the α-diimine compound with (DME)NiBr2 or (COD)PdMeCl is 1 to 50 h.

[0034] In the method for synthesizing pyridineimine nickel / palladium complexes with the chemical structures shown in formulas E-(II) and Z-(II) provided by the present invention, the molar ratio of formula E / Z-4 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1-6); the molar ratio of formula E / Z-8 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1-6).

[0035] In the synthesis methods of the imine nickel / palladium complexes with chemical structures shown in E-(I), Z-(I), E-(II), and Z-(II) provided by this invention, the imine compound represented by formula E / Z-4 or E / Z-8 is reacted with (DME)NiBr2 or (COD)PdMeCl in an organic solvent. The organic solvent is a solvent well-known to those skilled in the art, preferably a haloalkane, and more preferably dichloromethane. The molar ratio of the imine compound to (DME)NiBr2 is 1:(0.1–6). In specific embodiments, the molar ratio of the imine compound to (DME)NiBr2 or (COD)PdMeCl is 1:(1–3). Preferably, the reaction is carried out at 0°C to 38°C for 1–50 h; in specific embodiments, the reaction time is 12–24 h.

[0036] The present invention also provides the application of imine nickel / palladium complexes having the chemical structures shown in E-(I), Z-(I), E-(II) and Z-(II) in the synthesis of polyolefins.

[0037] In some embodiments provided by the present invention, the method further includes: irradiating the photoresponsive nickel / palladium complex with ultraviolet light before adding a catalytic amount of the photoresponsive nickel / palladium complex to the olefin polymerization system.

[0038] In some embodiments provided by the present invention, the wavelength of the ultraviolet light is 365nm or 405nm.

[0039] In some embodiments provided by this invention, the application includes: contacting a compound containing a terminal alkenyl group with an imine nickel / palladium complex having the chemical structures shown in E-(I), Z-(I), E-(II), and Z-(II), and an alkylaluminum reagent, thereby causing the compound containing the terminal alkenyl group to undergo a homopolymerization reaction. In this application, the homopolymerization reaction is carried out in an organic solvent, and after irradiating the compound shown in formulas E-(I) and Z-(I) with ultraviolet light, it is used as a catalyst to catalyze the polymerization reaction of ethylene to obtain a polyethylene product; the wavelength of the ultraviolet light is 365 nm or 405 nm, and the amount of the complex used in this application is 5–40 μmol·L. -1 The homopolymerization reaction temperature is 0℃~150℃, the pressure is 0.1~2.0MPa, and the reaction time is 0.05~3.00h.

[0040] In the application of this invention, the photoresponse behavior of the E-type catalyst was first investigated. In the UV absorption spectrum, under irradiation with a 365 nm UV lamp, the E-type catalyst exhibited a double peak around 350 nm, which is a characteristic absorption peak of rigid diphenylethylene. The absorption intensity of the double peaks weakened with increasing time. Furthermore, two isoabsorption points were observed, indicating that some E-type catalyst transformed into Z-type. Under irradiation with a 405 nm UV lamp, the Z-type catalyst showed only one peak around 350 nm. With increasing time, a double peak appeared, and the absorption intensity of the double peaks increased. Two isoabsorption points were also observed, indicating that some Z-type catalyst transformed into E-type. Based on the UV-Vis spectrum results, the irradiation time was determined.

[0041] In some embodiments provided by this invention, the application includes: contacting a compound containing a terminal alkenyl group, a polar monomer, an α-diimine nickel / palladium complex having the chemical structure shown in formula E-(I), and an alkylaluminum reagent, wherein the compound containing the terminal alkenyl group undergoes a copolymerization reaction with the polar monomer; the polar monomer refers to an olefin containing a heteroatom, including at least one of methyl 10-undecenoate, methyl acrylate, vinyltrimethoxysilane, propylene acetate, methyl norborneol, 6-chloro-1-hexene, and 10-undecenol. In this application, the copolymerization reaction temperature is 0–50°C, the copolymerization reaction pressure is 0.1–1.0 MPa, and the reaction time is 0.05–3.00 h. The concentration of the α-diimine nickel / palladium complex is 0.2–0.4 μmol·mL. -1 The monomer concentration is 0.1–3.0 M.

[0042] Preferably, in the above applications, the compound containing the terminal alkenyl group is an olefin, more preferably ethylene, and the alkyl aluminum reagent includes one or more of MAO, MMAO, AlMe3, AlEtCl2, AlEt2Cl, and AlEt3; the sodium borate is NaBArF.

[0043] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0044] 1. This photoresponsive nickel complex is stable at 120℃. It undergoes configurational inversion under two different wavelengths of ultraviolet light irradiation: from trans (E) to cis (Z) under 365nm ultraviolet light irradiation, and from cis (Z) to trans (E) under 405nm ultraviolet light irradiation. This demonstrates that the ratio between the E and Z configurations of the photoresponsive nickel complex can be precisely controlled using ultraviolet light irradiation. When used as a catalyst, this photoresponsive nickel complex can regulate the reaction rate in olefin polymerization, thereby achieving effective control over the molecular weight and polar monomer insertion rate of polyolefin materials.

[0045] 2. The polymer obtained by homopolymerization of ethylene catalyzed by the photoresponsive nickel / palladium complex provided by this invention is an elastomer with ultra-high molecular weight. Not only does the catalyst exhibit high catalytic activity in ethylene polymerization, but it also possesses good thermal stability. The resulting ultra-high molecular weight polyethylene has a molecular weight distribution of 1.60–2.57 and a molecular weight of 632–1184 × 10⁻⁶. 4 g·mol -1 Furthermore, it possesses excellent physical and mechanical properties, with an elastic recovery rate as high as 92%. The Z-configuration of the photoresponsive nickel / palladium complex provided by this invention allows for fewer branches in polyethylene, while the E-configuration allows for more branches. The Z-configuration results in a larger molecular weight for polyethylene, while the E-configuration results in a relatively smaller molecular weight. Simultaneously, compared to the E-configuration nickel complex, the photoresponsive Z-configuration nickel complex provided by this invention has unique advantages. A weak interaction exists between the ether chain and the bromine atom linked to metallic nickel, a characteristic that reduces the probability of poisoning and inactivation of the metal complex during copolymerization with polar monomers. Attached Figure Description

[0046] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0047] Figure 1 This is a single crystal structure diagram of E-(I)-3 provided in Embodiment 6 of the present invention.

[0048] Figure 2 A single crystal structure diagram of E-(I)-5 is provided for Embodiment 10 of the present invention.

[0049] Figure 3 This is a single crystal structure diagram of Z-(I)-5 provided in Embodiment 20 of the present invention.

[0050] Figure 4 The ultraviolet / visible spectra of E-(I)-1 to 5 and Z-(I)-5 provided in Embodiments 2, 4, 6, 8, 10 and 20 of the present invention are shown in the figures: a) E-(I)-1; b) E-(I)-2; c) E-(I)-3; d) E-(I)-4; e) E-(I)-5; f) Z-(I)-5.

[0051] Figure 5 The elastic recovery diagram of polyethylene prepared by E-(I)-1 provided in Application Example 2 of the present invention.

[0052] Figure 6 The elastic recovery diagram of polyethylene prepared by E-(I)-1 provided in Application Example 3 of the present invention.

[0053] Figure 7 The elastic recovery diagram of polyethylene prepared by E-(I)-2 provided in Application Example 5 of the present invention.

[0054] Figure 8 The elastic recovery diagram of polyethylene prepared by E-(I)-2 provided in Application Example 6 of the present invention.

[0055] Figure 9 The elastic recovery diagram of polyethylene prepared by E-(I)-3 provided in Application Example 8 of the present invention.

[0056] Figure 10 The elastic recovery diagram of polyethylene prepared by E-(I)-3 provided in Application Example 9 of the present invention.

[0057] Figure 11 The tensile stress-strain diagrams of polyethylene prepared by E-(I)-1 to 3 provided in Examples 1 to 9 of this invention are shown.

[0058] Figure 12 The ultraviolet / visible spectra of E-(II)-1 (left) and E-(II)-2 (right) provided in Embodiments 22 and 26 of the present invention are shown. Detailed Implementation

[0059] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0060] In this invention, the term "DME" represents dimethyl ethylene glycol ether; the term "compound containing terminal alkenyl groups" refers to small organic molecules with C=C double bonds at the ends, including alkenes, fatty acids containing terminal alkenyl groups, esters, etc. In α-diimine nickel / palladium complexes and pyridineimine nickel / palladium complexes, the "-" connected to Ni indicates a covalent bond or a coordinate bond.

[0061] Unless otherwise specified, the processes of homopolymerization and copolymerization are well known to those skilled in the art and will not be described in detail here.

[0062] The following embodiments illustrate different aspects of the invention. The data provided include ligand synthesis, metal complex synthesis, polymerization operations, polymerization conditions, and polymerization products. All operations, including reactions, preparations, and storage, were performed under a dry, inert atmosphere using standard Schlenk procedures. Molecular weight and molecular weight distribution were determined by GPC. Measurements were performed on an Agilent PL-200 instrument using trichlorobenzene as solvent and an Agilent PLgel Olexis column. Polyethylene was calibrated using Mark-Houwink parameters with general calibration, using polystyrene as a standard: K = 1.75 × 10⁻⁶. - 2 cm 3 ·g -1 R = 0.67 (polystyrene), K = 5.90 × 10⁻⁶ -2 cm 3 ·g -1 R = 0.69 (polyethylene).

[0063] In this invention, the preparation route of the imine compounds is as follows:

[0064] Unless otherwise specified, compounds E-4 / Z-4 and E-8 / Z-8 used in the following examples were prepared by the following method: under a nitrogen atmosphere, E-1 / Z-1 (1 mmol), commercially available compound 5 (2 mmol), and tetrakis(triphenylphosphine)palladium (0.2 mmol) were added to a 200 mL Schlenk flask, followed by the addition of 40 mL toluene, 4 mL ethanol, and 8 mL of saturated sodium carbonate aqueous solution. The reaction flask was then sealed and placed in a metal bath at 100 °C for 24 h. After the reaction was complete and the temperature returned to room temperature, the reaction system was extracted with dichloromethane and water, and the organic phase was concentrated to obtain a crude product. The crude product was purified by column chromatography (petroleum ether / dichloromethane = 1 / 1) to obtain a white solid E-2 / Z-2. Subsequently, under a nitrogen atmosphere, E-2 / Z-2 (1 mmol), compound 6 (CAS No.: 2750241-88-2) (1.5 mmol), and tetrakis(triphenylphosphine)palladium (0.2 mmol) were added to a 200 mL Schlenk flask, followed by 40 mL of toluene, 4 mL of ethanol, and 8 mL of saturated sodium carbonate aqueous solution. The reaction flask was sealed and placed in a metal bath at 100 °C for 24 h. After the reaction was complete and the temperature returned to room temperature, the reaction system was extracted with dichloromethane and water, and the organic phase was concentrated to obtain a crude product. The crude product was purified by column chromatography (petroleum ether / dichloromethane = 1 / 1) to obtain a white solid E-3 / Z-3. Among them, the R of compound 5... 1The substituents are H, CN, OCH2CH2OCH3, or monosubstituted phenyl. E-3 / Z-3 (0.75 mmol), compound 7 (0.94 mmol), and ZnCl2 (0.94 mmol) were added to a 25 mL Shrek flask, purged three times with nitrogen, and then glacial acetic acid (10 mL) was added. The mixture was stirred at 125 °C for 10 h under nitrogen protection. After the reaction was completed by TLC monitoring, the reaction was stopped, cooled to room temperature, and a yellow precipitate formed. The yellow precipitate was filtered and washed three times with glacial acetic acid and diethyl ether. The obtained solid was dissolved in 50 mL of dichloromethane, and saturated potassium oxalate aqueous solution (10 mL) was added and stirred for 12 h. The organic layer was extracted with dichloromethane (50 mL × 3), dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation to obtain the crude product. Subsequently, recrystallization from n-hexane solution yielded the corresponding pure compounds E-4 / Z-4 and R of compound 7. 2 The substituents are CH3, OCH3, or F.

[0065] The following examples illustrate the specific synthesis methods of the nickel / palladium complex:

[0066] In an argon-atmospheric glove box, the prepared imine ligand compounds E-4 / Z-4 (1.00 mmol), (DME)NiBr2 / (COD)PdMeCl (1.00 mmol), and 10 mL of anhydrous dichloromethane were added to a 50 mL round-bottom flask, and the mixture was stirred at room temperature for 24 h. After the reaction was complete, the solvent was removed under vacuum, and the reaction system was filtered through a hexane solution. The solid was recrystallized from the dichloromethane and hexane solutions to obtain the complex.

[0067] The reaction route is shown below:

[0068]

[0069] Example 1

[0070]

[0071] The specific synthesis of nickel complex E-(I)-1 ligand E-4-1: In the above reaction route, R of formula E-4 1 Substituents are H, R 2 When the substituent is CH3, the nickel complex E-(I)-1 ligand E-4-1 is prepared, with a yield of 69%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1H NMR (600MHz, CDCl3): δ7.84-7.83(m,2H),7.85-7.64(m,2H),7.48-7.44(m,4H),7.41-7. 35(m,5H),7.28-7.25(m,8H),7.21-7.18(m,4H),7.11-7.10(m,4H),7.06-7.04(m,4H),6 .66(s,2H),5.26(s,2H),3.33-3.30(m,4H),3.20-3.17(m,4H),2.67(hept,J=6.9Hz,2H) ,2.18(s,3H),1.91(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.91(s,3H)ppm. 13 C{1H}NMR (151MHz, CDCl3): δ169.9,168.0,146.3,145.7,145.6,145.4,143.9,143.71,143.68,142 .5,142.0,140.7,139.8,137.3,135.9,135.4,135.3,131.7,131.4,129.7,129.4,128.78,128.76, 128.4,128.1,127.3,127.1,126.34,126.31,126.25,126.1,125.2,125.1,123.4,123.2,122.1,52 .3,32.4,32.1,30.9,30.8,28.3,23.4,23.2,21.3,16.9,16.0ppm.HRMS(ESI-TOF)m / z:[M+H]+calcd for C 73 H 69 N2 + ,973.5456; found,973.5471.

[0072] Example 2

[0073] The specific synthesis method of nickel complex E-(I)-1:

[0074]

[0075] In an argon-atmospheric glove box, 1.00 mmol of the α-diimine compound E-4-1 prepared in Example 1, 1.00 mmol of (DME)NiBr2, and 10 mL of anhydrous dichloromethane were added to a 50 mL round-bottom flask, and the mixture was stirred at room temperature for 24 h. After the reaction was complete, the solvent was removed under vacuum, and the reaction system was filtered through a hexane solution. The solid was recrystallized from the dichloromethane and hexane solutions to obtain the solid nickel complex E-(I)-1, with a yield of 74%. ESI-MS (m / z): [M-Br] + calcd forC 73 H 68 BrN2Ni + ,1109.3914; found,1109.3934.

[0076] Example 3

[0077]

[0078] The specific synthesis of nickel complex E-(I)-2 ligand E-4-2: R of formula E-4 1 Substituents are H, R 2 When the substituent is OCH3, the yield of compound E-4-2 is 67%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3): δ7.84-7.83(m,2H),7.85-7.64(m,2H),7.48-7.44(m,4H),7.41-7. 35(m,5H),7.28-7.26(m,8H),7.21-7.17(m,4H),7.12-7.11(m,4H),7.07-7.05(m,4H),6 .44(s,2H),5.27(s,2H),3.56(s,3H),3.32-3.30(m,4H),3.20-3.17(m,4H),2.66(hept, J=7.0Hz,2H),1.90(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.94(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3): δ170.5,168.1,155.2,146.4,145.8,145.4,144.0,143.7,143.3,142 .3,142.0,141.7,140.7,139.8,137.4,135.9,135.5,135.3,132.9,129.7,129.4,128.8,128 .5,128.2,127.3,127.1,126.5,126.3,126.3,125.2,125.1,123.4,123.2,122.2,114.0,55. 2,52.5,32.5,32.2,30.94,30.87,28.4,23.5,23.2,16.9,16.1ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 73 H 69 N2O + ,989.5405; found,989.5417.

[0079] Example 4

[0080] Synthesis of nickel complex E-(I)-2:

[0081]

[0082] The preparation method was the same as in Example 2, except that the α-diimine compound E-4-2 prepared in Example 3 was added to obtain E-(I)-2, with a yield of 75%. ESI-MS (m / z): [M-Br] + calcd for C 73 H 68 BrN2NiO + ,1125.3863; found,1125.3850.

[0083] Example 5

[0084]

[0085] The specific synthesis of nickel complex E-(I)-3 ligand E-4-3: R of formula E-4 1 Substituents are H, R 2 With substituent F, the yield of compound E-4-3 was 67%; it was a yellow solid. Characterization data for this yellow solid are as follows: 1H NMR (600MHz, CDCl3): δ7.84(s,1H),7.82(s,1H),7.65-7.64(m,2H),7.48-7.44(m,4H),7 .44-7.35(m,5H),7.29-7.26(m,8H),7.23-7.19(m,4H),7.10-7.09(m,4H),7.05-7.04(m ,4H),6.60-6.58(m,2H),5.26(s,2H),3.33-3.29(m,4H),3.20-3.17(m,4H),2.65(hept, J=6.9Hz,2H),1.90(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.92(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ170.7,167.9,159.0(d, 1 J CF =240.2Hz),146.4,145.8,145.3,143.94,143.92,143.8,142.8,142.0,141.8,140.6,139.9,137.5,135.9,135.5,135.3,133.6(d, 3 J CF =6.6Hz),129.6,129.4,128.8,128.6,128.3,127.3,127.1,126.7,126.5,126.33,126.30,125.2,125.1,123.4,123.2,122.2,115.1(d, 2 J CF =23.3Hz),52.4,32.5,32.2,30.93,30.87,28.4,23.5,23.2,16.9,16.1ppm. 19 F{ 1 H}NMR(565MHz,CDCl3):δ-120.24ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 72 H 66 FN2 + ,977.5205;found,977.5218.

[0086] Example 6

[0087] Synthesis of nickel complex E-(I)-3:

[0088]

[0089] The preparation method was the same as in Example 2, except that the α-diimine compound E-4-3 prepared in Example 5 was added to obtain E-(I)-3, with a yield of 75%. ESI-MS (m / z): [M-Br] + calcd for C 73 H 65 BrFN2Ni + ,1113.3663; found,1113.3648.

[0090] Example 7

[0091]

[0092] The specific synthesis of nickel complex E-(I)-4 ligand E-4-4: R of formula E-4 1 Substituents are CN, R 2 When the substituent is CH3, the yield of compound E-4-4 is 55%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3) δ7.82 (d, J = 4.8Hz, 2H), 7.76-7.73 (m, 4H), 7.47-7.40 (m, 1H), 7.47-7.40 ( m,4H),7.37(s,2H),7.28-7.26(m,6H),7.20-7.18(m,4H),7.11(d,J=7.1Hz,4H),7.05(d,J=7. 7Hz,4H),6.66(s,2H),5.26(s,2H),3.34-3.28(m,4H),3.22-3.18(m,4H),2.67(hept,J=6.9Hz ,2H),2.18(s,3H),1.91(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.91(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3) δ169.8,168.1,147.9,146.5,145.8,145.6,145.5,144.4,143.7,143.5 ,142.6,140.8,137.8,137.3,136.6,135.4,134.9,132.6,131.8,131.4,129.8,129.5,128.8,1 28.5,128.1,127.8,126.6,126.4,126.1,125.6,125.2,123.30,123.28,122.1,119.1,110.7, 52.3,32.5,32.1,31.0,30.8,28.4,23.5,23.2,21.3,16.9,16.1ppm.HRMS(ESI-TOF)m / z:[M+K] + calcd for C 74 H 67 N3K + ,1036.4967;found,1036.4978.

[0093] Example 8

[0094] Synthesis of nickel complex E-(I)-4:

[0095]

[0096] The preparation method was the same as in Example 2, except that the α-diimine compound E-4-4 prepared in Example 7 was added to obtain E-(I)-4, with a yield of 60%. ESI-MS (m / z): [M-Br] + calcd for C 74 H 67 BrN3Ni + ,1134.3866; found,1134.4000.

[0097] Example 9

[0098]

[0099] The specific synthesis of nickel complex E-(I)-5 ligand E-4-5: R of formula E-4 1 The substituent is OCH2CH2OCH3, R 2 When the substituent is CH3, the yield of compound E-4-5 is 51%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1H NMR (600MHz, CDCl3) δ7.82-7.80(m,2H),7.57-7.56(m,2H),7.45-7.44(m,1H),7.40-7.36(m,5H),7.2 8-7.24(m,8H),7.20-7.18(m,4H),7.11(d,J=7.1Hz,4H),7.05-7.03(m,6H),6.66(s,2H),5.26(s,2H), 4.19-4.18(m,2H),3.80-3.78(m,2H),3.48(s,3H),3.32-3.30(m,4H),3.18-3.15(m,4H),2.67(hept, J=6.9Hz,2H),2.17(s,3H),1.91(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.91(s,3H)ppm. 13 C{ 1 H}NMR(151MHz,CDCl3)δ169.9,168.0,158.3,145.80,145.76,145.7,145.4,143.9,143.8,143.7,1 42.6,140.7,139.4,137.4,135.8,135.6,135.3,134.8,131.8,131.5,129.8,129.5,128.8,128.5,1 28.3,128.1,126.4,126.3,126.1,125.9,125.2,125.1,123.2,123.0,122.2,115.0,71.1,67.5,59. 3,52.3,32.5,32.2,30.89,30.87,28.4,23.5,23.2,21.3,16.9,16.1ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 76 H 75 N2O2 + ,1047.5824;found,1047.5837.

[0100] Example 10

[0101] Synthesis of nickel complex E-(I)-5:

[0102]

[0103] The preparation method was the same as in Example 2, except that the α-diimine compound E-4-5 prepared in Example 9 was added to obtain E-(I)-5, with a yield of 90%. ESI-MS (m / z): [M-Br] + calcd for C 76 H 74 BrN2NiO2 + ,1183.4282; found,1183.4289.

[0104] Example 11

[0105]

[0106] The specific synthesis of nickel complex Z-(I)-1 ligand Z-3-1: R of formula Z-4 1 Substituents are H, R 2 When the substituent is CH3, the yield of compound Z-4-1 is 52%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28 -7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6 .66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept,J=6.9Hz,2 H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141.2 ,141.1,139.7,138.4,137.0,135.3,135.2,135.1,133.8,131.7,131.4,129.8,129.4,128.8,12 8.4,128.1,128.0,126.4,126.3,126.1,126.0,125.4,125.3,122.1,122.0,121.3,114.8,52.3, 35.1,34.9,30.4,30.3,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H]+calcd for C 73 H 69 N2 + ,973.5456;found,973.5462.

[0107] Example 12

[0108] Synthesis of nickel complex Z-(I)-1:

[0109]

[0110] The preparation method was the same as in Example 2, except that the α-diimine compound Z-4-1 prepared in Example 11 was added to obtain Z-(I)-1, with a yield of 68%. ESI-MS (m / z): [M-Br] + calcd for C 73 H 68 BrN2Ni + ,1109.3914; found,1109.3943.

[0111] Example 13

[0112]

[0113] The specific synthesis of nickel complex Z-(I)-2 ligand Z-4-2: R of formula Z-4 1 Substituents are H, R 2 When the substituent is OCH3, the yield of compound Z-4-2 is 53%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28 -7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6 .66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept,J=6.9Hz,2 H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141. 2,141.1,139.7,138.4,137.0,135.3,135.2,135.1,133.8,131.7,131.4,129.8,129.4,128.8 ,128.4,128.1,128.0,126.4,126.3,126.1,126.0,125.4,125.3,122.1,122.0,121.3,114.8, 52.3,35.1,34.9,30.4,30.3,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 73 H 69 N2O + ,989.5405;found,989.5412.

[0114] Example 14

[0115] Synthesis of nickel complex Z-(I)-2:

[0116]

[0117] The preparation method was the same as in Example 2, except that the α-diimine compound Z-4-2 prepared in Example 13 was added to obtain Z-(I)-2, with a yield of 77%. ESI-MS (m / z): [M-Br] + calcd for C 73 H68 BrN2NiO + ,1125.3863; found,1125.3868.

[0118] Example 15

[0119]

[0120] The specific synthesis of nickel complex Z-(I)-3 ligand Z-4-3: R of formula Z-4 1 The substituent is H, and the R of compound 6 2 With the substituent F, the yield of compound Z-4-3 was 52%; it was a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7 .28-7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m ,4H),6.66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept, J=6.9Hz,2H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141. 2,141.1,139.7,138.4,137.0,135.3,135.2,135.1,133.8,131.7,131.4,129.8,129.4,128.8 ,128.4,128.1,128.0,126.4,126.3,126.1,126.0,125.4,125.3,122.1,122.0,121.3,114.8, 52.3,35.1,34.9,30.4,30.3,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 72 H 66 FN2 +,977.5205;found,977.5214.

[0121] Example 16

[0122] Synthesis of nickel complex Z-(I)-3:

[0123]

[0124] The preparation method was the same as in Example 2, except that the α-diimine compound Z-4-3 prepared in Example 15 was added to obtain Z-(I)-3, with a yield of 75%. ESI-MS (m / z): [M-Br] + calcd for C 73 H 65 BrFN2Ni + ,1113.3663;found,1113.3677.

[0125] Example 17

[0126]

[0127] The specific synthesis of nickel complex Z-(I)-4 ligand Z-4-4: R of formula Z-4 1 Substituents are CN, R 2 When the substituent is CH3, the yield of compound Z-4-4 is 54%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28 -7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6 .66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept,J=6.9Hz,2 H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141.2 ,141.1,139.7,138.4,137.0,135.3,135.24,135.21,133.8,131.7,131.4,129.8,129.4,128.8, 128.4,128.1,128.0,126.4,126.3,126.1,126.0,125.41,125.37,122.1,122.0,121.3,114.8,5 2.3,35.1,34.9,30.42,30.35,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+K] + calcd for C 74 H 67 N3K + ,1036.4967;found,1036.4972.

[0128] Example 18

[0129] Synthesis of nickel complex Z-(I)-4:

[0130]

[0131] The preparation method was the same as in Example 2, except that the α-diimine compound Z-4-4 prepared in Example 17 was added to obtain Z-(I)-4, with a yield of 60%. ESI-MS (m / z): [M-Br] + calcd for C 74 H 67 BrN3Ni + ,1134.3866;found,1134.3878.

[0132] Example 19

[0133]

[0134] Specific synthesis of nickel complex Z-(I)-5 ligand: R of formula Z-4 1 The substituent is OCH2CH2OCH3, R 2 When the substituent is CH3, the yield of compound Z-4-5 is 55%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28-7.27(m,4H ),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6.66-6.64(m,4H),5.23(s ,2H),3.96-3.94(m,2H),3.59-3.58(m,2H),3.32(s,3H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hep t,J=6.9Hz,2H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141.2,141 .1,139.7,138.4,137.0,135.3,135.24,135.21,133.8,131.7,131.4,129.8,129.4,128.8,128.4,12 8.1,128.0,126.4,126.3,126.1,126.0,125.41,125.37,122.1,122.0,121.3,114.8,71.0,67.2,59 .1,52.3,35.1,34.9,30.42,30.35,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 76 H 75 N2O2 + ,1047.5824;found,1047.5831.

[0135] Example 20

[0136] Synthesis of nickel complex Z-(I)-5:

[0137]

[0138] The preparation method was the same as in Example 2, except that the α-diimine compound Z-4-5 prepared in Example 19 was added to obtain Z-(I)-5, with a yield of 90%. ESI-MS (m / z): [M-Br] + calcd for C 76 H 74 BrN2NiO2 + ,1183.4282;found,1183.4275.

[0139] As attached Figure 2 and Figure 3 As shown, analysis of the E-(I)-5 and Z-(I)-5 single crystals revealed a wealth of valuable data. Specifically, the distance between Br2 and H11 in the E-(I)-5 single crystal is... In Z-(I)-5 single crystal, however, It is worth noting that both of these distance values ​​are smaller than the sum of the van der Waals radii of Br and H. Meanwhile, the distance between Br1 and H24 shows a clear changing trend, from that in E-(I)-5 Shortened to Z-(I)-5 Furthermore, regarding bond angles, in the E-(I)-5 single crystal, the angle formed by Br2-Ni1-Br1 is 118.20°, while in the Z-(I)-5 single crystal, the corresponding Br2-Ni1-Br1 angle increases to 123.21°. Also, the distance between H(H73) and Br(Br1) is... The aforementioned key distance and angle data strongly suggest the existence of weak hydrogen bond interactions between CH···Br-M, providing solid evidence and strong support for the existence of these interactions in the system.

[0140] This invention provides specific synthetic steps for the pyridineimine compound E / Z-8:

[0141] Similar to the preparation method of α-diimine compounds E-4 / Z-4, compound 7 was replaced with compound 9, and recrystallization from n-hexane solution yielded the corresponding pure compounds E-8 / Z-8. The preparation method for the metal complex E-(II) / Z-(II) is also consistent with that for the diimine complex. The reaction route is shown below:

[0142]

[0143] Example 21

[0144]

[0145] The specific synthesis of nickel complex E-(II)-1 ligand E-8-1: R of formula E-8 1 When the substituent is H, the yield of compound E-8-1 is 83%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3): δ8.69(s,1H),8.39(d,J=8.1Hz,1H),7.85(d,J=9.7Hz,2H),7.83-7.80(m,1H),7.64-7.63(m,2H ),7.48-7.34(m,10H),3.34-3.29(m,4H),3.19-3.16(m,4H),2.86-2.79(m,2H),2.29(s,3H),1.24-1.22(m,12H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.2,156.5,148.6,146.4,145.8,145.7,144.0,1 43.7,142.0,140.8,139.8,137.2,136.5,136.2,136.0,135.4,128.8,127.3 ,127.1,126.4,126.3,125.2,125.1,124.8,123.4,123.3,122.2,121.4,32. 5,32.2,30.94,30.88,28.5,23.4,23.0,17.6ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 43 H 43 N2 + ,587.3421;found,587.3417.

[0146] Example 22

[0147] Synthesis of nickel complex E-(II)-1:

[0148]

[0149] The method was the same as in Example 2, except that the pyridineimide compound E-8-1 prepared in Example 21 was added to obtain E-(II)-1 in 90% yield. ESI-MS (m / z): [M-Br] + calcd for, C 43 H 42 BrN2Ni + ,723.1879; found,723.1889.

[0150] Example 23

[0151]

[0152] Specific synthesis of nickel complex Z-(II)-1 ligand Z-8-1: R of formula Z-8 1 When the substituent is H, the yield of compound Z-8-1 is 71%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3): δ8.67(d,J=4.2Hz,1H),8.50(s,1H),8.44(s,1H),8 .37-8.35(m,1H),7.82-7.79(m,1H),7.47-7.46(m,1H),7.41-7.39(m,2H) ,7.37-7.34(m,4H),7.31(s,2H),7.16-7.10(m,3H),3.07-3.03(m,4H),2 .91-2.88(m,4H),2.73-2.67(m,2H),2.22(s,3H),1.06-1.04(m,12H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.0,156.5,148.6,147.4,146.8,145.7,141.3, 141.1,139.8,138.9,136.7,136.5,136.2,135.4,135.0,128.6,127.0,126 .8,126.5,126.3,125.41,125.39,124.8,122.0,122.0,121.9,121.4,35.1 ,34.9,30.44,30.41,28.5,23.3,22.7,17.5ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 43 H 43 N2 + ,587.3421;found,587.3437.

[0153] Example 24

[0154] Synthesis of nickel complex Z-(II)-1:

[0155]

[0156] The method was the same as in Example 2, except that the pyridineimide compound Z-8-1 prepared in Example 23 was added to obtain Z-(II)-1 in 90% yield. ESI-MS (m / z): [M-Br] +calcd for, C 43 H 42 BrN2Ni + ,723.1879; found,723.1883.

[0157] Example 25

[0158]

[0159] The specific synthesis of nickel complex E-(II)-2 and palladium complex E-(II)-3 ligand E-8-2: R of formula E-8 1 When the substituent is Ph, the yield of compound E-8-2 is 87%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1 H NMR (600MHz, CDCl3): δ8.69(d,J=4.8Hz,1H),8.39(d,J=7.9Hz,1H),7.89(s,1H),7.86(s,1H),7.84-7.81(m,1H),7.73-7.69(m,4H),7.66-7.65(m ,2H),7.49-7.45(m,4H),7.41-7.35(m,6H),3.34-3.33(m,4H),3.20-3.1 8(m,4H),2.82(hept,J=6.8Hz,2H),2.29(s,3H),1.24-1.22(m,12H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.2,156.5,148.6,146.5,145.8,145.7,144.0,143.7 ,140.9,140.84,140.82,140.0,139.3,137.2,136.5,136.2,136.0,135.4,128.8, 127.6,127.5,127.3,127.1,126.4,126.1,125.3,125.1,124.8,123.3,122.2,12 1.4,32.5,32.2,31.0,30.9,28.5,23.3,23.0,17.5ppm.HRMS(ESI-TOF)m / z:[M+H] + calcdfor C 49 H 47 N2 + ,663.3734;found,663.3741.

[0160] Example 26

[0161] Synthesis of nickel complex E-(II)-2:

[0162]

[0163] The method was the same as in Example 2, except that the pyridineimide compound E-8-2 prepared in Example 25 was added to obtain E-(II)-2 in 90% yield. ESI-MS (m / z): [M-Br] + calcd for, C 49 H 46 BrN2Ni + ,799.2192; found,799.2195.

[0164] Example 27

[0165] Synthesis of palladium complex E-(II)-3:

[0166]

[0167] In an argon-atmospheric glove box, 1.00 mmol of the pyridineimine compound E-8-2 prepared in Example 25, 1.00 mmol of (COD)PdMeCl, and 10 mL of anhydrous dichloromethane were added to a 50 mL round-bottom flask, and the mixture was stirred at room temperature for 24 h. After the reaction was complete, the solvent was removed under vacuum, and the reaction system was filtered through a hexane solution. The solid was recrystallized from the dichloromethane and hexane solutions to obtain the solid complex E-(II)-3, with a yield of 89%. ESI-MS (m / z): [M-Br] + calcd forC 49 H 46 BrN2Ni + ,783.2925; found,783.2935.

[0168] Example 28

[0169]

[0170] Specific synthesis of nickel complex Z-(II)-2 and palladium complex Z-(II)-3 ligand Z-8-2: R of formula Z-8 1 When the substituent is Ph, the yield of the compound is 70%; it is a yellow solid. Characterization data for this yellow solid are as follows: 1H NMR (600MHz, CDCl3): δ8.66-8.65(m,1H),8.54(s,1H),8.51(s,1H),8.32-8.31m,1H) ,7.77-7.74(m,1H),7.60-7.58(m,2H),7.48-7.47(m,1H),7.45-7.44(m,3H),7.39-7 .34(m,7H),7.33(s,2H),7.30-7.28(m,1H),3.07-3.04(m,4H),2.92-2.89(m,4H),2. 70(hept,J=6.9Hz,2H),2.19(s,3H),1.05(d,J=6.9Hz,6H),0.98(d,J=6.9Hz,6H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.0,156.5,148.6,147.5,146.8,145.7,141.3,141.1,14 0.7,140.0,139.9,139.5,138.3,136.8,136.4,136.2,135.5,135.0,128.6,127.4,12 7.3,127.1,126.9,126.5,126.2,125.5,125.4,124.7,122.3,122.1,121.7,121.4,3 5.1,34.9,30.44,30.43,28.5,23.2,22.8,17.4ppm.HRMS(ESI-TOF)m / z:[M+H]+calcd for C 49 H 47 N2 + ,663.3734;found,663.3744.

[0171] Example 29

[0172] Synthesis of nickel complex Z-(II)-2:

[0173]

[0174] The method was the same as in Example 2, except that the pyridineimide compound Z-8-2 prepared in Example 28 was added to obtain Z-(II)-2, 90%. ESI-MS (m / z): [M-Br] + calcd for C 49 H 46 BrN2Ni + ,799.2192;found,799.2199.

[0175] Example 30

[0176] Synthesis of nickel complex Z-(II)-3:

[0177]

[0178] The method was the same as in Example 27, except that the pyridineimide compound Z-8-2 prepared in Example 28 was added to obtain Z-(II)-3 in 88% yield. ESI-MS (m / z): [M-Br] + calcd for C 49 H 46 BrN2Ni + ,783.2925; found,783.2933.

[0179] Application Examples 1 to 9 show that imine nickel complexes E-(I)-1 to 3 with different substituents exhibit different catalytic characteristics in the homopolymerization of ethylene at different temperatures: under ethylene pressure of 0.8 MPa, dark conditions, and different temperatures, this type of catalyst has high catalytic activity and ultra-high molecular weight in ethylene polymerization, which also indicates that the catalyst has high temperature resistance.

[0180] Application Example 1

[0181] Under anhydrous and oxygen-free conditions in a glove box, 48 mL of anhydrous toluene was added to a 100 mL thick-walled quartz dish and then placed in an intelligent olefin polymerization apparatus. The reactor was evacuated, and ethylene was introduced until saturation. AlEt₂Cl (0.5 mL, 1 M intoluene) was then added. After preheating and stirring at 30 °C, a 2 mL solution of dichloromethane containing 1 μmol of α-diimine nickel complex E-(I)-1 was added, and the ethylene pressure was adjusted to 0.8 MPa. The reaction was stirred for 10 min. After the reaction, the reactants were quenched with an ethanol solution containing 5% hydrochloric acid. The polymer was precipitated, filtered, washed, and then vacuum dried at 50 °C to constant weight to obtain the polymerization product. Specific experimental results are shown in Table 1.

[0182] Application Example 2

[0183] The experimental procedure was the same as in Application Example 1, except that the reaction temperature was changed from 30℃ to 50℃. The results are shown in Table 1.

[0184] Application Example 3

[0185] The experimental procedure was the same as in Application Example 1, except that the reaction temperature was changed from 30℃ to 80℃. The results are shown in Table 1.

[0186] Table 1

[0187]

[0188] Application Examples 1-3 demonstrate the catalytic performance of the E-(I)-1 catalyst at different temperatures under a pressure of 0.8 MPa and a reaction time of 10 min. The catalyst remains active at 80 °C, demonstrating its high-temperature resistance. The molecular weight of the E-(I)-1 catalyst decreases with increasing temperature. This is because the chain transfer rate increases at higher temperatures, leading to a decrease in molecular weight and an increase in branching.

[0189] Application Example 4

[0190] The experimental procedure was the same as in Application Example 1, except that the catalyst was changed from E-(I)-1 to E-(I)-2, as shown in Table 2.

[0191] Application Example 5

[0192] The experimental procedure is the same as in Application Example 4, except that the reaction temperature is changed from 30℃ to 50℃, as shown in Table 2.

[0193] Application Example 6

[0194] The experimental procedure is the same as in Application Example 4, except that the reaction temperature is changed from 30℃ to 80℃, as shown in Table 2.

[0195] Table 2

[0196]

[0197]

[0198] Application Examples 4-6 demonstrate the catalytic performance of the E-(I)-2 catalyst at different temperatures under a pressure of 0.8 MPa and a reaction time of 10 min. The catalyst remains active at 80 °C, showcasing its high-temperature resistance. Compared to the E-(I)-1 catalyst, the E-(I)-2 catalyst has a methoxy substituent, resulting in a slightly higher molecular weight. The molecular weight of the E-(I)-2 catalyst tends to decrease with increasing temperature.

[0199] Application Example 7

[0200] The experimental procedure was the same as in Application Example 1, except that the catalyst was changed from E-(I)-1 to E-(I)-3, as shown in Table 3.

[0201] Application Example 8

[0202] The experimental procedure is the same as in Application Example 7, except that the reaction temperature is changed from 30℃ to 50℃, as shown in Table 3.

[0203] Application Example 9

[0204] The experimental procedure is the same as in Application Example 7, except that the reaction temperature is changed from 30℃ to 80℃, as shown in Table 3.

[0205] Table 3

[0206]

[0207] Application Examples 7-9 demonstrate the catalytic performance of the E-(I)-3 catalyst at different temperatures under a pressure of 0.8 MPa and a reaction time of 10 min. Compared to E-(I)-1, the E-(I)-3 catalyst has an F substituent. The F substituent interacts with the β-H on the polymer, resulting in a slight increase in molecular weight. The molecular weight of the E-(I)-3 catalyst decreases with increasing temperature. This is because the electron-withdrawing F group is easily affected by temperature, leading to an increased chain transfer rate, decreased molecular weight, and slightly increased branching. Furthermore, the polymer obtained by homopolymerization of ethylene catalyzed by catalyst E-(I)-3 at 50℃ exhibits an elastic recovery rate as high as 92%, as shown in the attached figure. Figure 9 As shown.

[0208] Application Examples 10–27 show that imine nickel complexes with different substituents exhibit different catalytic characteristics during ethylene homopolymerization under different light conditions: compared with the dark condition, the E-type catalyst after light irradiation has higher catalytic activity, higher molecular weight and lower branching degree in ethylene polymerization.

[0209] The photoisomerization behavior of nickel catalysts was investigated in depth by detecting changes in the UV-Vis absorption spectrum in dichloromethane solution (see appendix). Figure 4 Under ultraviolet light irradiation at a wavelength of 365 nm, the absorbance of E-(I)-1, E-(I)-2, and E-(I)-3 gradually decreases within the wavelength range of 252 nm to 359 nm. Among them, E-(I)-5 with a lone pair of electrons (oxygen atom) or E-(I)-4 containing a cyano group can form a conjugated system with the π bond of the benzene ring. This conjugation effect greatly promotes the occurrence of p-π conjugation. This interaction essentially broadens the range of electron activity, significantly improves the excitation efficiency, and consequently causes a redshift of the π→π* transition absorption band towards longer wavelengths.

[0210] For E-(I)-4, its absorbance shows a gradually decreasing trend in the wavelength range of 262nm to 362nm; similarly, E-(I)-5 also shows a gradually decreasing trend in absorbance in the wavelength range of 256nm to 361nm. However, in stark contrast, when Z-(I)-5 is irradiated with visible light at a wavelength of 405nm, its absorbance shows a gradually increasing trend.

[0211] The characteristic absorption peaks of rigid diphenylethylene are around 325nm to 365nm. E-(I)-5 has two peaks at this point, and the absorption intensity decreases with the extension of 365nm UV lamp irradiation time. Z-(I)-5, on the other hand, has only one peak at this point, and with the extension of 405nm UV lamp irradiation time, two peaks appear, and the UV absorption intensity increases.

[0212] Notably, isoabsorption points were observed at approximately 256 nm and 361 nm in the UV-Vis absorption spectra of both E-(I)-5 and Z-(I)-5. This phenomenon strongly demonstrates the interconversion capability between the two isomers under illumination, providing crucial experimental evidence for in-depth research on their photochemical properties and related reaction mechanisms. Furthermore, the E-configuration catalyst requires a longer time to reach photosteady state and a shorter UV irradiation wavelength than the Z-configuration catalyst, verifying that the E-configuration has lower thermodynamic energy and greater structural stability.

[0213] Application Example 10

[0214] The procedure was the same as in Application Example 1, except that anhydrous toluene was replaced with anhydrous dichloromethane (30 mL), the ethylene pressure was adjusted to 0.2 MPa, the reaction time was adjusted to 30 min, and the reaction temperature was adjusted to 0 °C. The specific experimental results are shown in Table 4.

[0215] Application Example 11

[0216] According to the appendix Figure 4 The UV-Vis absorption spectra revealed that the E-(I) catalyst reached a stable state after irradiation with 365 nm UV light for 420 seconds, with no further conversion from the E configuration to the Z configuration. Therefore, the irradiation time of the catalyst before polymerization was determined to be 10 minutes. The experimental procedure was the same as in Application Example 10, except that the catalyst E-(I)-1 was added to the reaction system after 10 minutes of 365 nm UV irradiation. The specific experimental results are shown in Table 4.

[0217] Table 4

[0218]

[0219] Application Examples 10-11 demonstrate the catalytic performance of the E-(I)-1 catalyst at 0°C under a pressure of 0.2 MPa and a reaction time of 30 min. Compared to no light exposure, the E-(I)-1 catalyst exhibits higher activity after light exposure, resulting in a decrease in chain transfer rate, an increasing molecular weight, and a reduction in branching degree.

[0220] Application Example 12

[0221] The experimental procedure was the same as in Application Example 10, except that the catalyst was changed from E-(I)-1 to E-(I)-2, as shown in Table 5.

[0222] Application Example 13

[0223] The experimental procedure was the same as in Application Example 11, except that the catalyst was changed from E-(I)-1 to E-(I)-2, as shown in Table 5.

[0224] Table 5

[0225]

[0226] Application Examples 12-13 demonstrate the catalytic performance of the E-(I)-2 catalyst at 0°C under a pressure of 0.2 MPa and a reaction time of 30 min. Compared to no light exposure, the E-(I)-2 catalyst exhibits higher activity after light exposure, resulting in a decrease in chain transfer rate, an increasing molecular weight, and a reduction in branching degree.

[0227] Application Example 14

[0228] The experimental procedure was the same as in Application Example 10, except that the catalyst was changed from E-(I)-1 to E-(I)-3, as shown in Table 6.

[0229] Application Example 15

[0230] The experimental procedure was the same as in Application Example 11, except that the catalyst was changed from E-(I)-1 to E-(I)-3, as shown in Table 6.

[0231] Table 6

[0232]

[0233] Application Examples 14-15 demonstrate the catalytic performance of the E-(I)-3 catalyst at 0°C under a pressure of 0.2 MPa and a reaction time of 30 min. Compared to no light exposure, the E-(I)-3 catalyst exhibits higher activity after light exposure, resulting in a decrease in chain transfer rate, an increasing molecular weight, and a reduction in branching degree.

[0234] Application Example 16

[0235] The experimental procedure was the same as in Application Example 10, except that the catalyst was changed from E-(I)-1 to E-(I)-4, as shown in Table 7.

[0236] Application Example 17

[0237] The experimental procedure was the same as in Application Example 11, except that the catalyst was changed from E-(I)-1 to E-(I)-4, as shown in Table 7.

[0238] Table 7

[0239]

[0240]

[0241] Application Examples 16-17 demonstrate the catalytic performance of the E-(I)-4 catalyst at 0°C under a pressure of 0.2 MPa and a reaction time of 30 min. Compared to no light exposure, the E-(I)-4 catalyst exhibits higher activity after light exposure, resulting in a decrease in chain transfer rate, an increasing molecular weight, and a reduction in branching degree.

[0242] Application Example 18

[0243] The experimental procedure was the same as in Application Example 10, except that the catalyst was changed from E-(I)-1 to E-(I)-5, as shown in Table 8.

[0244] Application Example 19

[0245] The experimental procedure was the same as in Application Example 11, except that the catalyst was changed from E-(I)-1 to E-(I)-5, as shown in Table 8.

[0246] Application Examples 18-19 demonstrate the catalytic performance of the E-(I)-5 catalyst at 0°C under a pressure of 0.2 MPa and a reaction time of 30 min. Compared to no light exposure, the E-(I)-5 catalyst exhibits higher activity after light exposure due to the weak interaction between the hydrogen atoms on the ether chain of the Z-type catalyst and the bromine atoms on the nickel metal. This results in a decrease in the chain transfer rate, an increase in molecular weight, and a reduction in branching degree.

[0247] Table 8

[0248]

[0249] Application Example 20

[0250] The experimental procedure is the same as in Application Example 18, except that the reaction temperature is changed from 0℃ to room temperature, as shown in Table 9.

[0251] Application Example 21

[0252] The experimental procedure is the same as in Application Example 19, except that the reaction temperature is changed from 0℃ to room temperature, as shown in Table 9.

[0253] Table 9

[0254]

[0255] Application Examples 20-21 demonstrate the catalytic performance of the E-(I)-5 catalyst at room temperature under a pressure of 0.2 MPa and a reaction time of 30 min. Compared to the unilluminated state, the E-(I)-5 catalyst exhibits similar activity and molecular weight after illumination; however, due to partial conversion of the E-form to the Z-form configuration after irradiation with 405 nm UV light, the weak interaction between the hydrogen atoms on the ether chain of the Z-form catalyst and the bromine atoms bonded to metallic nickel leads to a decrease in the branching degree of the polymer.

[0256] Application Example 22

[0257] The procedure was the same as in Application Example 1, except that the volume of anhydrous toluene solvent was changed to 18.5 mL, the ethylene pressure was adjusted to 0.2 MPa, and the reaction was stirred for 60 min, as shown in Table 10.

[0258] Application Example 23

[0259] According to the appendix Figure 12 The UV-Vis absorption spectra revealed that the E-(II)-1 or E-(II)-2 catalysts exhibited a stable state after irradiation with 365 nm UV light for 210 seconds, with no further conversion from the E configuration to the Z configuration. Therefore, the irradiation time of the catalyst before polymerization was determined to be 5 minutes. The experimental procedure was the same as in Application Example 22, except that the added catalyst E-(II)-1 needed to be irradiated with 365 nm UV light for 5 minutes before being added to the reaction system. The specific experimental results are shown in Table 10.

[0260] Table 10

[0261]

[0262] Application Examples 22-23 demonstrate the catalytic performance of the E-(II)-1 catalyst at room temperature under a pressure of 0.2 MPa and a reaction time of 60 min. Compared to the unilluminated state, the E-(II)-1 catalyst exhibits similar activity and molecular weight after illumination, with no significant difference.

[0263] Application Example 24

[0264] The experimental procedure was the same as in Application Example 22, except that the catalyst was changed from E-(II)-1 to E-(II)-2, as shown in Table 11.

[0265] Application Example 25

[0266] The experimental procedure was the same as in Application Example 23, except that the catalyst was changed from E-(II)-1 to E-(II)-2, as shown in Table 11.

[0267] Table 11

[0268]

[0269] Application Examples 24-25 demonstrate the catalytic performance of the E-(II)-2 catalyst at room temperature under a pressure of 0.2 MPa and a reaction time of 60 min. Compared to the unilluminated state, the E-(II)-1 catalyst exhibits relatively higher activity and molecular weight after illumination, possibly due to the interaction between the benzene ring on the ligand and nickel, leading to a decrease in the transfer rate, an increasing molecular weight, and a slight decrease in the degree of branching.

[0270] Application Example 26

[0271] Under anhydrous and oxygen-free conditions in a glove box, NaBArF (2 eq.) and anhydrous dichloromethane (38 mL) were added to a 350 mL thick-walled reaction flask. The reaction vessel was then evacuated, and ethylene was introduced until saturation. After pre-stirring, a dichloromethane solution containing 10 μmol of catalyst E-(II)-3 (2 mL) was added, and the ethylene pressure was adjusted to 0.4 MPa. The reaction was stirred for 180 min. After the reaction was completed, the product was dried under vacuum at 50 °C to constant weight to obtain the polymerization product. Specific results are shown in Table 12.

[0272] Application Example 27

[0273] The experimental procedure was the same as in Application Example 26, except that the catalyst E-(II)-3 was added to the reaction system after being irradiated with 365nm ultraviolet light for 5 minutes. The specific experimental results are shown in Table 12.

[0274] Table 12

[0275]

[0276] Application Examples 26-27 demonstrate the catalytic performance of the E-(II)-3 catalyst at room temperature under a pressure of 0.4 MPa and a reaction time of 180 min. Compared to the unilluminated state, the E-(II)-3 catalyst exhibits relatively higher activity and molecular weight after illumination, possibly due to the weak interaction between the benzene ring on the ligand and the palladium metal, leading to a decrease in the transfer rate, an increasing molecular weight, and a slight decrease in the degree of branching.

[0277] The 27 application examples mentioned above are examples of ethylene homopolymerization.

[0278] Application Examples 28–39 show that the imine nickel complex E-(I)-5 exhibits different activities and insertion rates in the copolymerization of ethylene with polar monomers.

[0279] Application Examples 28-33

[0280] According to the appendix Figure 4The UV-Vis absorption spectrum results showed that the E-(I) catalyst exhibited a stable state after irradiation with 365nm UV light for 420 seconds, and there was no longer a conversion from the E configuration to the Z configuration. Furthermore, since the concentration of the catalyst required for the copolymerization reaction was relatively high, the irradiation time of the catalyst before polymerization was determined to be 20 minutes.

[0281] Under anhydrous and oxygen-free conditions in a glove box, a polar enol monomer, anhydrous toluene, and AlEt2Cl (5 mL, 1 M in toluene) were added sequentially to a 350 mL thick-walled reaction flask. The pressure-resistant flask was removed from the glove box and connected to the ethylene gas line. After evacuation, ethylene was introduced until saturation. The mixture was stirred for 10 min at 0.2 MPa and room temperature. Then, a solution of 10 μmol of α-diimine nickel complex E-(I)-5 in dichloromethane (2 mL) was added, either under no light or under light for 20 min. The mixture was stirred for 30 min. The reaction was terminated with ethanol containing 5% hydrochloric acid after completion. The polymer was precipitated, filtered, washed, and then vacuum dried at 50 °C to constant weight to obtain the polymer product. Specific experimental results are shown in Table 13.

[0282] Table 13

[0283]

[0284]

[0285] Applications 28-33 demonstrate the catalytic performance of the E-(I)-5 catalyst in copolymerizing ethylene with enol polar monomers at room temperature under a pressure of 0.2 MPa and a reaction time of 30 min. Comparing Applications 28 and 29, the E-(I)-5 nickel catalyst exhibits deactivation with increasing polar monomer concentration because the polar monomer is Lewis basic while the metal complex is Lewis acidic. However, as in Examples 29 and 30, the E-(I)-5 catalyst partially transforms from the E-form to the Z-form configuration after light irradiation. The weak interaction between the hydrogen atoms on the ether chain of the Z-form catalyst and the bromine atoms bonded to the nickel metal results in a lower probability of poisoning and deactivation during copolymerization with polar monomers, thus demonstrating activity.

[0286] Application Examples 34-39

[0287] The procedure is the same as in Application Examples 28-33, except that the enol polar monomer is replaced with an olefinic polar monomer, as shown in Table 14.

[0288] Table 14

[0289]

[0290] Experimental results show that Application Examples 34–39 demonstrate the catalytic copolymerization performance of E-(I)-5 catalyst with different olefinic polar monomers at room temperature under a pressure of 0.2 MPa and a reaction time of 30 min. The polymer results are consistent with the analysis in Table 13.

[0291] The nickel complex provided by this invention can achieve catalytic homopolymerization of ethylene or copolymerization with polar monomers, and achieve controllable catalytic activity under ultraviolet light irradiation, producing polyolefin materials with adjustable molecular weight and polar monomer insertion rate.

[0292] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A photoresponsive mononuclear imine nickel / palladium complex of ultra-high molecular weight polyethylene was prepared, having the chemical structures shown in formulas E-(I), Z-(I), E-(II), and Z-(II): Where R 1 It is one of hydrogen, cyano, OCH2CH2OCH3, or phenyl; R 2 It is one of hydrogen, halogen, or methoxy; M is one of the metals Ni or Pd. The imine-type nickel / palladium complex can undergo configurational transformation under ultraviolet light irradiation of two different wavelengths: under 365 nm ultraviolet light irradiation, it transforms from the trans configuration (E) to the cis configuration (Z), and under 405 nm ultraviolet light irradiation, it transforms from the cis configuration (Z) to the trans configuration (E).

2. The method for preparing photoresponsive mononuclear imine nickel / palladium complexes for ultra-high molecular weight polyethylene according to claim 1, characterized in that, The chemical structure shown in formula E-(I) α - Diimine nickel / palladium complexes include at least one of E-(I)-1 to E-(I)-5, and pyridineimine nickel / palladium complexes with the chemical structure shown in formula E-(II) include at least one of E-(II)-1 to E-(II)-3, and pyridineimine nickel / palladium complexes with the chemical structure shown in formula Z-(I) α - Diimine nickel / palladium complexes include at least one of Z-(I)-1 to Z-(I)-5, and pyridineimine nickel / palladium complexes with the chemical structure shown in formula Z-(II) include at least one of Z-(II)-1 to Z-(II)-3: 。 3. The method for preparing the photoresponsive mononuclear imine nickel / palladium complex of ultra-high molecular weight polyethylene according to claim 1 or 2, characterized in that, Includes the following steps: a. Compound E-1 or Z-1 and compound 5 undergo a Suzuki coupling reaction at 80–120 °C under the catalysis of a second catalyst to generate compound E-2 or Z-2; compound E-2 or Z-2 and compound 6 undergo a Suzuki coupling reaction at 80–120 °C under the catalysis of a second catalyst to generate aniline compound E-3 or Z-3; compound 7 and aniline compound E-3 or Z-3 undergo a condensation reaction at 80–120 °C under the catalysis of a third catalyst to generate compound E-4 or Z-4. α - Diimine compounds; b. As shown in formula E-4 or Z-4 α -Diimine compounds react with (DME)NiBr2 or (COD)PdMeCl at 0–45 °C to produce compounds with the chemical structures shown in E-(I) or Z-(I). α -Diimine nickel / palladium complex; The reaction route is shown below: Among them, R 1 It is one of hydrogen, cyano, OCH2CH2OCH3, or phenyl, R 2 It is one of hydrogen, halogen, and methoxy; The second catalyst is tetra(triphenylphosphine)palladium or 1,1'-bis(diphenylphosphine)ferrocene palladium(II); The third catalyst is zinc dichloride or p-toluenesulfonic acid.

4. The preparation method according to claim 3, characterized in that: The molar ratio of compound E-1 or Z-1 to compound 5 is (1~2):1; the molar ratio of compound E-2 or Z-2 to compound 6 is (1~2):1; the molar ratio of compound 7 to compound E-3 or Z-3 is (1~2):1; and the molar ratio of compound E-4 or Z-4 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1~6).

5. The method for synthesizing photoresponsive mononuclear imine nickel / palladium complexes for ultra-high molecular weight polyethylene according to claim 1 or 2, characterized in that, Includes the following steps: a. Compound 9 is condensed with the compound shown in formula E-3 or Z-3 at 80~120 °C under the catalysis of a fourth catalyst to generate the pyridineimine compound shown in formula E-8 or Z-8. b. React the pyridineimine compound represented by formula E-8 or Z-8 with (DME)NiBr2 or (COD)PdMeCl at 0~45 °C to generate pyridineimine nickel / palladium complexes having the chemical structures shown by formulas E-(II) and Z-(II); The reaction route is as follows: Among them, R 1 It is one of hydrogen, cyano, OCH2CH2OCH3, and phenyl; The fourth catalyst is zinc dichloride or p-toluenesulfonic acid.

6. The synthesis method according to claim 5, characterized in that: The molar ratio of compound 9 to the compound shown in formula E-3 or Z-3 is (1~2):1; the molar ratio of the compound shown in formula E-8 or Z-8 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1~6).

7. An application of the photoresponsive mononuclear nickel / palladium complex for preparing ultra-high molecular weight polyethylene as described in claim 1 or 2 in the catalytic synthesis of polyolefin materials, characterized in that: A catalytic amount of a photoresponsive mononuclear nickel / palladium complex was added to the olefin polymerization system as a catalyst, and the polymerization reaction was carried out at a temperature of 0 °C to 150 °C. For the ethylene homopolymerization system, a compound containing terminal alkenyl groups was contacted with a photoresponsive mononuclear nickel / palladium complex having the chemical structure shown in formula E-(I) or E-(II), an alkyl aluminum, or a sodium borate reagent. The compound containing terminal alkenyl groups underwent homopolymerization under the catalysis of the catalyst. The homopolymerization reaction was carried out in an organic solvent, and the amount of the photoresponsive mononuclear nickel / palladium complex was 5–40 μmol·L⁻¹. -1 The homopolymerization reaction was carried out at a temperature of 0–150 °C, a pressure of 0.1–2.0 MPa, and a reaction time of 0.05–3.00 h. For the ethylene copolymerization system, a compound containing terminal alkenyl groups, a polar monomer, and a photoresponsive mononuclear nickel / palladium complex with the chemical structure shown in formula E-(I) or E-(II), along with alkyl aluminum or sodium borate reagent, were contacted. The compound containing terminal alkenyl groups and the polar monomer underwent a copolymerization reaction at a temperature of 0–50 °C, a pressure of 0.1–1.0 MPa, and a reaction time of 0.05–3.00 h. The concentration of the photoresponsive mononuclear nickel / palladium complex was 200–400 μmol·L⁻¹. -1 The monomer concentration is 0.1~3.0 M; the polar monomer refers to a monomer containing heteroatoms. α - An olefin, which is at least one of methyl 10-undecenoate, vinyltrimethoxysilane, 6-chloro-1-hexene, 10-undecenol, methyl acrylate, propylene acetate, and methyl norbornenoate. Before adding a catalytic amount of the photoresponsive nickel / palladium complex to the olefin polymerization system, E-(I) or E-(II) is irradiated with ultraviolet light at a wavelength of 365 nm.

8. The application according to claim 7, characterized in that: The photoresponsive mononuclear nickel / palladium complex serves as a highly active and thermally stable catalyst for the polymerization of ethylene to prepare ultra-high molecular weight polyethylene thermoplastic elastomers. The ultra-high molecular weight polyethylene has a molecular weight distribution of 1.60–2.57 and a molecular weight of 632–1184 × 10⁻⁶. 4 g·mol -1 It also has good physical and mechanical properties, with an elastic recovery rate of up to 92%.

Images