CN112961193B - Linear magnetic tetranuclear nickel complex and preparation method and application thereof - Google Patents

Linear magnetic tetranuclear nickel complex and preparation method and application thereof Download PDF

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CN112961193B
CN112961193B CN202110223152.8A CN202110223152A CN112961193B CN 112961193 B CN112961193 B CN 112961193B CN 202110223152 A CN202110223152 A CN 202110223152A CN 112961193 B CN112961193 B CN 112961193B
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tetranuclear
linear magnetic
nickel complex
nickel
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CN112961193A (en
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汪力
武晋娣
黄剑
苏碧云
赵赛迪
王文珍
代芳平
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Xian Shiyou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7095—Cobalt, nickel or compounds thereof
    • C08F4/7098—Nickel or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a linear magnetic tetranuclear nickel complex, a preparation method and application thereof, and belongs to the technical field of multifunctional new materials. The linear magnetic tetranuclear nickel complex has the structural formula:the preparation method of the linear magnetic tetranuclear nickel complex has the advantages of readily available raw materials, simple preparation process, less time consumption, mild reaction conditions and high yield when being applied to catalyzing the synthesis of cyclic carbonate and the polymerization of methyl methacrylate, and has wide industrial application prospects in catalyzing carbon dioxide to generate cyclic carbonate and catalyzing the polymerization of methyl methacrylate, and good catalytic activity and application value.

Description

Linear magnetic tetranuclear nickel complex and preparation method and application thereof
Technical Field
The invention belongs to the technical field of multifunctional new materials, and relates to a linear magnetic tetranuclear nickel complex, a preparation method and application thereof.
Background
CO 2 Not only is considered to be the main greenhouse gas responsible for global warming, but also represents an inexhaustible, inexpensive and nontoxic source of C1, which can be used as a surrogate raw material for fossil fuels. CO 2 Coupling with epoxides to give cyclic carbonates reduces CO 2 Environmental protection reaction of discharging and saving energy is accepted by industryAnd a great importance of chemists. Especially under mild conditions, the production cost and the energy consumption can be reduced. Therefore, the catalysis of carbon dioxide to form cyclic carbonate is one of the research hotspots, and the synergistic effect between metal centers in the polynuclear complex can be controlled to synthesize the high-performance catalyst.
In recent years, polymethyl methacrylate (PMMA) has attracted attention as one of the most widely used polymers, and a catalytic metal system catalyzes the polymerization of Methyl Methacrylate (MMA). A great deal of effort has been devoted to the development of structurally defined metal complexes. For a given metal complex catalytic system, the ligand plays an important role in the reaction. Suitable ligands may increase the activity and controllability of the catalyst. Accordingly, efforts have been made to design new ligands that are cheaper, more readily available and exhibit better catalytic properties. However, in the current technology, the ligand synthesis process is complex, the cost is too high, the yield is low, and the synthesized catalyst has poor stability and low activity.
In summary, it is necessary to study a novel catalyst for catalyzing cycloaddition of carbon dioxide and MMA polymerization, which has good catalytic performance, and can reduce production cost and energy consumption and save energy.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the linear magnetic tetranuclear nickel complex, and the preparation method and application thereof, and the linear magnetic tetranuclear nickel complex with high catalytic efficiency and excellent stability is prepared by the preparation method with simple process and low cost investment, so that the problems of high cost and low catalyst activity are solved.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a linear magnetic tetranuclear nickel complex, which has the following structural formula:
preferably, the linear magnetismThe tetranuclear nickel complex has a crystal structure, and the crystallographic data of the tetranuclear nickel complex are as follows: the crystal belongs to monoclinic system, and the space group is P2 1 N; unit cell parameters: α＝90°，β＝111.8860(10)°，γ＝90°，/>Dc＝1.601g/cm 3 z= 4,F (000) = 2552.0, μ (MoKa) =0.71073, goof=1.067, crystal size: 0.2mm by 0.12mm by 0.1mm, R 1 ＝0.0735，wR 2 ＝0.1768，
The invention discloses a preparation method of a linear magnetic tetranuclear nickel complex, which comprises the following steps:
uniformly dispersing the ligand in a reaction solvent, continuously adding nickel salt for carrying out a coordination reaction after deprotonation treatment to obtain a solution mixed system, filtering the obtained solution mixed system to obtain filtrate, and drying the obtained filtrate to obtain the linear magnetic tetranuclear nickel complex;
wherein the ligand has the following structural formula:
preferably, the ratio of the ligand to the mass of the nickel salt is 1:1 to 1:2.
preferably, the reaction solvent is a mixed solution of acetonitrile and methanol, wherein the mixed volume ratio of acetonitrile to methanol is 1:1 to 1:6.
preferably, the nickel salt is one or more of nickel chloride, nickel acetate, nickel nitrate, nickel sulfate.
Preferably, the temperature of the compounding reaction is room temperature (15 to 35 ℃) for 15 to 30 minutes.
Preferably, the operation of the drying process includes: naturally volatilizes for 7 to 14 days at room temperature (15 to 35 ℃) or dries for 30 to 40 hours at 60 to 70 ℃ in a high-temperature oven.
Preferably, the base used for deprotonation is one or two of sodium hydroxide, triethylamine, potassium hydroxide and lithium hydroxide.
The invention discloses an application of the linear magnetic tetranuclear nickel complex or the linear magnetic tetranuclear nickel complex prepared by the preparation method as a catalyst.
Preferably, the linear magnetic tetranuclear nickel complex is used for catalyzing carbon dioxide to generate cyclic carbonate.
Preferably, the linear magnetic tetranuclear nickel complex is applied to catalyzing the polymerization of methyl methacrylate.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a linear magnetic tetranuclear nickel complex, which takes acylhydrazone Schiff base as a ligand and has a tetranuclear structure, wherein the linear magnetic tetranuclear nickel complex has good molecular structure stability, has a large coordination cavity through the controllable design of the ligand, can have good catalytic performance, can effectively coordinate with N and O atoms with certain coordination capability through nickel atoms, avoids the use of noble metals, and has the advantage of high stability, thus having extremely high popularization and use values.
The invention also discloses a preparation method of the linear magnetic tetranuclear nickel complex, which takes the acylhydrazone Schiff base as a ligand, has a large coordination cavity, can ensure that the finally prepared linear magnetic tetranuclear nickel complex has a plurality of coordination points, and has the advantages of simple reaction conditions, quick reaction, energy conservation, time conservation and no pollution. Therefore, the preparation method of the linear magnetic tetranuclear nickel complex has the advantages of high yield which can reach 61%, low ligand consumption and cost saving, and is beneficial to large-scale production.
Furthermore, the preparation method disclosed by the invention is suitable for preparing and using common compounds, and the cost input is effectively controlled.
Furthermore, by utilizing the characteristic that the reaction can be carried out at room temperature in a short time, the problems of complex process and high cost of preparing the linear magnetic tetranuclear nickel complex are solved, and the efficient reaction is realized.
The invention also discloses application of the linear magnetic tetranuclear nickel complex as a catalyst. The linear magnetic tetranuclear nickel complex has good magnetic property and catalytic property because the central nickel atom has no unpaired electron and has good empty electron orbit and is easy to accept electron pairs, can be applied to catalyzing carbon dioxide conversion and PMMA polymerization, provides an alternative material in the magnetic and catalytic fields, and has the advantages of less time consumption, mild reaction condition and high yield.
Drawings
FIG. 1 is a schematic view of the crystal structure of the linear magnetic tetranuclear nickel complex prepared in example 1;
FIG. 2 is an infrared emission spectrum of the linear magnetic tetranuclear nickel complex prepared in example 1 of the present invention;
FIG. 3 is an ultraviolet-visible absorption spectrum of the linear magnetic tetranuclear nickel complex prepared in example 1 of the present invention;
FIG. 4 shows the ligand of the linear magnetic tetranuclear nickel complex of the present invention 1 H NMR chart;
FIG. 5 shows the ligand of the linear magnetic tetranuclear nickel complex of the present invention 13 C NMR chart;
FIG. 6 is a magnetic diagram of a linear magnetic tetranuclear nickel complex prepared in example 1 of the present invention;
FIG. 7 is a graph showing the thermal stability analysis of the linear magnetic tetranuclear nickel complex prepared in example 1 of the present invention;
FIG. 8 is a nuclear magnetic resonance chart of the linear magnetic tetranuclear nickel complex catalyzed synthesis of cyclic carbonate in application example 1 of the present invention;
FIG. 9 is a nuclear magnetic resonance chart of the linear magnetic tetranuclear nickel complex catalyzed synthesis of cyclic carbonate in application example 5 of the present invention;
FIG. 10 is a nuclear magnetic resonance chart of the linear magnetic tetranuclear nickel complex catalyzed synthesis of cyclic carbonate in application example 6 of the present invention;
FIG. 11 is a nuclear magnetic resonance chart of the linear magnetic tetranuclear nickel complex catalyzed synthesis of cyclic carbonate in application example 7 of the present invention;
FIG. 12 is a nuclear magnetic resonance chart of the linear magnetic tetranuclear nickel complex catalyzed synthesis of cyclic carbonate in application example 8 of the present invention;
FIG. 13 is a nuclear magnetic resonance chart of the linear magnetic tetranuclear nickel complex catalyzed synthesis of cyclic carbonate in application example 9 of the present invention;
FIG. 14 is a nuclear magnetic resonance chart of the linear magnetic tetranuclear nickel complex catalyzed synthesis of cyclic carbonates according to application example 10 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is further described below with reference to specific examples and figures:
example 1
1.1 Linear magnetic tetranuclear Nickel Complex[Ni 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 And (3) preparation of O.
0.05mmol (13 mg) of ligand H was accurately weighed out using an analytical balance 2 L is added into a beaker, 12mL of mixed solution of methanol and acetonitrile (volume ratio is 1:1), stirring is carried out for 10min at room temperature and 25 ℃, 4mg of sodium hydroxide is added for deprotonation, 0.05mmol (12 mg) of nickel chloride hexahydrate is added for continuous stirring and matched reaction for 15min, dark red solution is obtained, standing and filtering are carried out, filtrate is placed into a glass bottle, standing is carried out for 36h in a vacuum drying oven at 65 ℃, and a reddish brown crystal-shaped nickel-based complex is obtained, namely the linear magnetic tetranuclear nickel complex, and the crystal size is basically about 0.2mm multiplied by 0.12mm multiplied by 0.1mm.
In other embodiments, the nickel salt may be replaced with nickel acetate (nickel acetate tetrahydrate), nickel nitrate (nickel nitrate hexahydrate), nickel sulfate (nickel sulfate hexahydrate) in addition to nickel chloride (nickel chloride hexahydrate).
The structural formula of the linear magnetic tetranuclear nickel complex product is as follows:in the linear magnetic tetranuclear nickel complex, ligand H 2 The structural formula L is as follows: />Which is a kind of 1 The H NMR chart is shown in FIG. 4, which shows that 13 The C NMR chart is shown in FIG. 5.
Elemental analysis (C) of the above-mentioned linear magnetic tetranuclear nickel complex 44 H 56 N 10 Ni 4 O 17 ): theoretical value (%): c,42.86; h,4.55; n,11.37; measured value (%): c,42.80; h,4.48; n,11.57;
referring to fig. 2, in the infrared emission spectrum of the linear magnetic tetranuclear nickel complex, the main IR absorption peak is: 1686cm -1 、1612.4cm -1 、1600.2cm -1 、1383.9cm -1 、1155.3cm -1 、971.6cm -1 、730.8cm -1 。
The linear magnetic tetranuclear nickel complex has a crystal structure and has crystallographic data: the crystal belongs to monoclinic system, and the space group is P2 1 N; unit cell parameters:α＝90°，β＝111.8860(10)°，γ＝90°，/>Dc＝1.601g/cm 3 z= 4,F (000) = 2552.0, μ (MoKa) =0.71073, goof=1.067, crystal size: 0.2mm 0.12mm 0.1mm R 1 ＝0.0735，wR 2 ＝0.1768。
1.2 determination of the Linear magnetic tetranuclear Nickel Complex Crystal Structure.
Single crystals of about 0.2mm x 0.12mm x 0.1mm in size were selected under a microscope and placed on an a Bruker APEX-ii CCD single crystal diffractometer for diffraction experiments, and 18391 diffraction points were collected at 296 (2) K using mokα rays (λ= 0.071073) in a range of 2.58 +.ltoreq.θ.ltoreq.25.05°, with 4546 individual diffraction points [ rint=0.0565, rsigma=0.0357 ], and 3342 observable diffraction points [ I >2σ (I) ] for structural analysis and structural correction. All data were corrected for Lp factor and empirical absorption. The crystal structure is solved by a direct method through a SHELXS-97 procedure, the structure is refined through the SHELXL-97 procedure, and the hydrogen atoms and the non-hydrogen atoms are respectively corrected through a full matrix least square method through isotropic and anisotropic temperature factors. The final deviation factor r=0.06.
The molecular structure of the linear magnetic tetranuclear nickel complex is shown in figure 1, and the main bond lengths and bond angles are shown in table 1. From crystal structure FIG. 1, the title complex molecule consists of 4 nickel (II) ions, 2 ligands. Wherein two nickel (II) ions are coordinated with three nitrogen atoms and one oxygen atom from two ligands respectively to form a four-coordinated nickel atom; another nickel ion is coordinated with one nitrogen atom, three oxygen atoms, one water molecule and one methanol molecule in the two ligands to form six-coordination nickel ions; leaving one nickel ion with one nitrogen atom, three oxygen atoms and two water in the two ligandsThe molecules coordinate to form hexacoordinated nickel ions. Two tetradentate nickel ions, two hexadentate nickel ions and two ligands are coordinated to form [ Ni ] 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 Linear structure of O. The longest Ni-O bond length in the complex isThe shortest isThe longest bond length of Ni-N is +.>Shortest is +.>The maximum key angle is 176.14 ° and the minimum key angle is 81.54 °.
TABLE 1 major bond lengths of the complexesKey angle (°)
1.3 determination of spectral Properties of Linear magnetic tetranuclear Nickel Complex
Referring to fig. 2, the infrared spectrum of the linear magnetic tetranuclear nickel complex is measured, and the result shows that: (1) Ligand H 2 L coordinates with nickel (II), H 2 1686.0cm in L -1 、1612.4cm -1 The stretching vibration of C=N on the imino group is red shifted at 1600.2cm -1 Peak is formed; (2) 1383.9cm -1 is-CH 3 In-plane bending vibration of C-H; (3) 1155.3cm -1 、1077.8cm -1 Is C on benzene ring-in-plane bending vibration of H; (4) 971.6cm -1 、730.8cm -1 Is the out-of-plane bending vibration of hydrogen on the benzene ring.
Referring to fig. 3, the ultraviolet spectrum of the linear magnetic tetranuclear nickel complex is measured, and the result shows that: the absorption peaks of the ligand and the linear magnetic tetranuclear nickel complex are greatly different. Ligand H 2 L has three absorption peaks at 218nm, 294nm and 365nm, and is a conjugated system C=N in a molecule in the ligand. The coordination reaction is carried out on the ligand and C=N bond of the metal atom in the linear magnetic tetranuclear nickel complex, and energy level transition is carried out on pi- & gt pi-electrons of C=N, so that the peaks are subjected to red shift of 247nm, 316nm and 468nm.
1.4 measuring the magnetism of the linear magnetic tetranuclear nickel complex.
FIG. 6 is a magnetic analysis chart of the linear magnetic tetranuclear nickel complex: as shown in fig. a, the magnetization of the Ni (ii) complex as a function of temperature was recorded on the polycrystalline sample at a temperature range of 2-300K under a direct current magnetic field of 1 Koe. At 300K, χ M T value is a maximum of 3.70cm 3 ·K·mol -1 When cooling, when the temperature is reduced from 300K to 30K, χ M T value decreases slowly, and χ is reduced when the temperature is less than 30K M The T value drops rapidly. X at a temperature of 2K M T drops rapidly to a minimum of 1.44cm 3 ·K·mol -1 . This may be due to orbital contribution caused by thermal relaxation of the Stark sub-energy levels of the anisotropic Ni (II) ions, and may also result from antiferromagnetic interactions between adjacent Ni (II) ions. X-shaped articles M The general outline of the T-T diagram reveals the presence of antiferromagnetic exchange interactions within the chain. The magnetocaloric effect (MCE) of the above linear magnetic tetranuclear nickel complexes was evaluated, and they were isothermally magnetized at 2K in the range of 0-7T, as shown in fig. b. The M-H curve steadily increases with increasing magnetic field, and the M-H curve of the complex reaches 2.76 Nbeta at 2K and 7T.
1.5 analysis of thermal stability Property of Linear magnetic tetranuclear Nickel Complex
FIG. 7 is a thermal stability analysis of the linear magnetic tetranuclear nickel complex described above: in a nitrogen atmosphere, the temperature range is 25-800 ℃. No obvious mass loss below 300 ℃ and almost 0 weight loss, namely the linear magnetThe tetranuclear nickel complex has good thermal stability below 300 ℃ and can be decomposed at a temperature exceeding 300 ℃. Such thermogravimetric behavior indicates that fully deprotonated ligand H 2 L has a larger binding capacity to Ni (II) ions. Taking into account Ni 4 L 2 Excellent magnetic and catalytic properties, and its high stability in hot environments, ni 4 L 2 Has great potential application prospect as a magnetic and catalytic dual-functional material.
Example 2
Linear magnetic tetranuclear nickel complex [ Ni ] 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 And (3) preparation of O.
0.05mmol (13 mg) of ligand H was accurately weighed out using an analytical balance 2 L is put into a beaker, 14mL of mixed solution of methanol and acetonitrile (volume ratio is 1:6), stirring is carried out for 10min at 35 ℃, 13 mu L of triethylamine is added for deprotonation, 0.1mmol (25 mg) of nickel acetate tetrahydrate is added for continuous stirring and matched reaction for 10min, dark red solution is obtained, standing and filtering are carried out, filtrate is put into a glass bottle, standing is carried out for 40h in a vacuum drying oven at 60 ℃, and a reddish brown crystal-shaped nickel-based complex is obtained, namely the linear magnetic tetranuclear nickel complex, and the crystal size is basically about 0.2mm multiplied by 0.12mm multiplied by 0.1mm.
Example 3
Linear magnetic tetranuclear nickel complex [ Ni ] 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 And (3) preparation of O.
0.05mmol (13 mg) of ligand H was accurately weighed out using an analytical balance 2 L in a beaker, adding 16mL of mixed solution of methanol and acetonitrile (volume ratio of 1:3), stirring at 15 ℃ for 10min, adding 5.6mg of potassium hydroxide for deprotonation, adding 0.075mmol (20 mg) of nickel sulfate hexahydrate, continuously stirring for carrying out a complex reaction for 30min to obtain a dark red solution, standing, filtering, placing the filtrate in a glass bottle, standing for 30h in a vacuum drying oven at 70 ℃ to obtain a reddish brown crystal-like nickel-based complex, namely the linear magnetic tetranuclear nickel complex, wherein the crystal size is basically about 0.2mm multiplied by 0.12mm multiplied by 0.1mmAnd right.
Example 4
Linear magnetic tetranuclear nickel complex [ Ni ] 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 And (3) preparation of O.
0.05mmol (13 mg) of ligand H was accurately weighed out using an analytical balance 2 L is added into a beaker, 15mL of mixed solution of methanol and acetonitrile (volume ratio is 1:2), stirring is carried out for 10min at 20 ℃, 2.4mg of lithium hydroxide is added for deprotonation, 0.06mmol (17 mg) of nickel nitrate hexahydrate is added for continuous stirring for carrying out a matching reaction for 25min, a dark red solution is obtained, standing and filtering are carried out, filtrate is placed into a glass bottle, natural volatilization is carried out for 7 days at room temperature and 20 ℃ to obtain a reddish brown crystal-shaped nickel-based complex, namely the linear magnetic tetranuclear nickel complex, and the crystal size is basically about 0.2mm multiplied by 0.12mm multiplied by 0.1mm.
Example 5
Linear magnetic tetranuclear nickel complex [ Ni ] 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 And (3) preparation of O.
0.05mmol (13 mg) of ligand H was accurately weighed out using an analytical balance 2 L is added into a beaker, 18mL of mixed solution of methanol and acetonitrile (volume ratio is 1:5), stirring is carried out for 10min at 20 ℃, 2mg of sodium hydroxide and 7 mu L of triethylamine are added for deprotonation, 0.09mmol (26 mg) of nickel nitrate hexahydrate is added for continuous stirring for carrying out a matching reaction for 20min, a dark red solution is obtained, standing and filtering are carried out, filtrate is placed into a glass bottle and naturally volatilized for 14 days at room temperature of 35 ℃ to obtain a reddish brown crystal-shaped nickel-based complex, namely the linear magnetic tetranuclear nickel complex, and the crystal size is basically about 0.2mm multiplied by 0.12mm multiplied by 0.1mm.
Example 6
Linear magnetic tetranuclear nickel complex [ Ni ] 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 And (3) preparation of O.
0.05mmol (13 mg) of ligand H was accurately weighed out using an analytical balance 2 L in a beaker, add 14mL of methanol andthe mixed solution of acetonitrile (volume ratio is 1:6), stirring for 10min at 15 ℃, adding 4mg of sodium hydroxide for deprotonation, adding 0.1mmol (25 mg) of nickel acetate tetrahydrate, continuously stirring for carrying out a coordination reaction for 30min to obtain a dark red solution, standing, filtering, placing the filtrate in a glass bottle, and naturally volatilizing for 10 days at room temperature of 15 ℃ to obtain a reddish brown crystal-like nickel-based complex, namely the linear magnetic tetranuclear nickel complex, wherein the crystal size is basically about 0.2mm multiplied by 0.12mm multiplied by 0.1mm. The invention also discloses application of the linear magnetic tetranuclear nickel complex as a catalyst.
Specifically, the linear magnetic tetranuclear nickel complex can be applied to catalyzing carbon dioxide to generate cyclic carbonate and can also be applied to catalyzing MMA polymerization.
The following description of the catalytic performance analysis of the linear magnetic tetranuclear nickel complex according to the present invention is made with reference to specific application examples:
application example 1
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst, wherein the using amount of a cocatalyst TBAC (tetrabutylammonium chloride) is 0.5mol% of the using amount of the epoxy compound, and the substrate epoxy compound is 20mmol of epoxy styrene; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis showed 92% conversion and greater than 99% selectivity. The synthesis of which yields cyclic carbonates 1 The H NMR chart is shown in FIG. 8.
Application example 2
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 2 as a catalyst, wherein the using amount of a cocatalyst TBAAc (tetrabutylammonium acetate) is 0.5mol% of the using amount of the epoxy compound, and the substrate epoxy compound is 20mmol of epoxy styrene; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, and finally placing the high-pressure reaction kettleCooling to room temperature, discharging residual gas, sampling 1 The H NMR analysis shows that the conversion rate is 90% and the selectivity is more than 99%.
Application example 3
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 3 as a catalyst, wherein the consumption of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5mo1% of the consumption of the epoxy compound, and the substrate epoxy compound is 20mmol of epoxy styrene; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis shows that the conversion rate is 95% and the selectivity is more than 99%.
Application example 4
Taking the linear magnetic tetranuclear nickel complex prepared in the example 4 as a catalyst 4.8mg, wherein the dosage of a cocatalyst PPN-Cl (ditrityl ammonium chloride) is 0.5mo1% of the dosage of the epoxy compound, and the substrate epoxy compound is 20mmol of epoxy styrene; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis showed that the conversion was 79% and the selectivity was greater than 99%.
Application example 5
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst, wherein the consumption of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5mo1% of the consumption of the epoxy compound, and the substrate epoxy compound is 20mmol of epichlorohydrin; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis shows that the conversion rate is 98% and the selectivity is more than 99%. It is synthesized toTo cyclic carbonates 1 The H NMR chart is shown in FIG. 9.
Application example 6
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst, wherein the consumption of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5mo1% of the consumption of the epoxy compound, and the substrate epoxy compound is 20mmol of propylene oxide; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis shows that the conversion rate is 98% and the selectivity is more than 99%. The synthesis of which yields cyclic carbonates 1 The H NMR chart is shown in FIG. 10.
Application example 7
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst, wherein the consumption of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5mo1% of the consumption of the epoxy compound, and the substrate epoxy compound is 20mmol of cyclohexene oxide; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis showed that the conversion was 68% and the selectivity was greater than 99%. The synthesis of which yields cyclic carbonates 1 The H NMR chart is shown in FIG. 11.
Application example 8
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst, wherein the consumption of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5mo1% of the consumption of the epoxy compound, and the substrate epoxy compound is 20mmol of allyl glycidyl ether; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis shows that the conversion rate is 90% and the selectivity is more than 99%. The synthesis of which yields cyclic carbonates 1 The H NMR chart is shown in FIG. 12.
Application example 9
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst, wherein the consumption of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5mo1% of the consumption of the epoxy compound, and the substrate epoxy compound is 20mmol of phenyl glycidyl ether; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis shows that the conversion rate is 95% and the selectivity is more than 99%. The synthesis of which yields cyclic carbonates 1 The H NMR chart is shown in FIG. 13.
Application example 10
Taking 4.8mg of the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst, wherein the consumption of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5mo1% of the consumption of the epoxy compound, and the substrate epoxy compound is 20mmol of isopropyl glycidyl ether; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis showed 92% conversion and greater than 99% selectivity. The synthesis of which yields cyclic carbonates 1 The H NMR chart is shown in FIG. 14.
Application example 11
4.8mg of a reactant after the linear magnetic tetranuclear nickel complex prepared in the example 5 is used as a catalyst for recycling for 1 time, the using amount of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5 mmol of the using amount of the epoxy compound, and the substrate epoxy compound is 20mmol of epoxy styrene; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle at 120 DEG CIn the constant temperature heating sleeve of (2), reacting for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, sampling and utilizing 1 The H NMR analysis shows that the conversion rate is 93% and the selectivity is more than 99%.
Application example 12
4.8mg of a reactant after the linear magnetic tetranuclear nickel complex prepared in the example 6 is used as a catalyst for recycling for 5 times, the using amount of a cocatalyst TBAB (tetrabutylammonium bromide) is 0.5 mmol of the using amount of the epoxy compound, and the substrate epoxy compound is 20mmol of epoxy styrene; adding the catalyst, the cocatalyst and the substrate into a 50mL high-pressure reaction kettle, and filling 1Mpa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve at 120 ℃ for reaction for 1h, finally cooling the high-pressure reaction kettle to room temperature, discharging residual gas, and sampling and utilizing 1 The H NMR analysis showed 92% conversion and greater than 99% selectivity.
In summary, in the above embodiments, the linear magnetic tetranuclear nickel complex uses the acylhydrazone Schiff base as the ligand, has a tetranuclear structure, has good molecular structure stability, has good catalytic performance, can be used as a catalyst to catalyze the cycloaddition of carbon dioxide to generate cyclic carbonate, and widens the selection range of catalytic materials. The preparation process of the linear magnetic tetranuclear nickel complex has the advantages of simple operation, mild reaction conditions, low-cost and easily-obtained materials, and uniform obtained crystal particles.
Application example 13
The linear magnetic tetranuclear nickel complex prepared in example 1 is taken as a catalyst 19mg, a cocatalyst AIBN (azodiisobutyronitrile) 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is carried out firstly, nitrogen is filled again, after three times of circulation, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are pumped into the three-neck flask by a syringe with scales, and finally rubber tubes on two sides are clamped by hemostatic forceps. Reacting at 100deg.C in electrothermal sleeve for 0.25 hr, adding 5% acid ethanol as terminator 1-2mL to terminate the reaction, and adding 50mL ethanol is placed. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 0.5778 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 0.7986 ×10 4 g·mol -1 The relative molecular mass distribution was 5.7402.
Application example 14
The linear magnetic tetranuclear nickel complex prepared in the example 1 is taken as a catalyst 19mg, a cocatalyst AIBN 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is performed firstly, nitrogen is then filled, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are injected by a syringe with scales after three times of circulation, and finally rubber tubes on two sides are clamped by hemostatic forceps. And (3) carrying out reaction for 0.5h in an electrothermal sleeve at 100 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after finishing the reaction, and then adding 50mL of ethanol for standing. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 4.8924 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 1.9745 ×10 4 g·mol -1 The relative molecular mass distribution was 5.7211.
Application example 15
The linear magnetic tetranuclear nickel complex prepared in the example 1 is taken as a catalyst 19mg, a cocatalyst AIBN 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is performed firstly, nitrogen is then filled, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are injected by a syringe with scales after three times of circulation, and finally rubber tubes on two sides are clamped by hemostatic forceps. And (3) carrying out reaction for 0.75h in an electrothermal sleeve at 100 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after finishing the reaction, and then adding 50mL of ethanol for standing. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 0.3513 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 5.6587 ×10 4 g·mol -1 The relative molecular mass distribution was 2.5035.
Application example 16
The linear magnetic tetranuclear nickel complex prepared in the example 1 is taken as a catalyst 19mg, a cocatalyst AIBN 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is performed firstly, nitrogen is then filled, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are injected by a syringe with scales after three times of circulation, and finally rubber tubes on two sides are clamped by hemostatic forceps. And (3) carrying out reaction for 1h in an electrothermal sleeve at 100 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after finishing the reaction, and then adding 50mL of ethanol for standing. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 2.6918 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 4.5801 ×10 4 g·mol -1 The relative molecular mass distribution was 2.0879.
Application example 17
The linear magnetic tetranuclear nickel complex prepared in the example 1 is taken as a catalyst 19mg, a cocatalyst AIBN 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is performed firstly, nitrogen is then filled, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are injected by a syringe with scales after three times of circulation, and finally rubber tubes on two sides are clamped by hemostatic forceps. And (3) carrying out reaction for 2 hours in an electrothermal sleeve at 100 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after finishing the reaction, and then adding 50mL of ethanol for standing. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 1.3067 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 0.8716 ×10 4 g·mol -1 The relative molecular mass distribution was 10.8673.
Application example 18
Taking the linear magnetic tetranuclear nickel complex prepared in the example 1 as a catalyst 19mg, a promoter AIBN 20mg and a rotor, adding the mixture into a dried three-neck flask, sealing the upper mouth of the three-neck flask, connecting the other two mouths with a vacuum pump and a nitrogen bag through rubber tubes respectively, vacuumizing and then filling nitrogen, circulating for three times, and using a beltA graduated syringe was then filled with a dry quantity of MMA (2 mL) and toluene (5 mL), and finally the rubber tube was clamped on both sides with hemostats. And (3) carrying out reaction for 0.5h in an electrothermal sleeve at 120 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after finishing the reaction, and then adding 50mL of ethanol for standing. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 0.6122 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 1.3246 ×10 4 g·mol -1 The relative molecular mass distribution was 5.9716.
Application example 19
The linear magnetic tetranuclear nickel complex prepared in the example 1 is taken as a catalyst 19mg, a cocatalyst AIBN 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is performed firstly, nitrogen is then filled, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are injected by a syringe with scales after three times of circulation, and finally rubber tubes on two sides are clamped by hemostatic forceps. And (3) carrying out reaction for 0.5h in an electrothermal sleeve at 110 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after finishing the reaction, and then adding 50mL of ethanol for standing. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 4.5945 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 4.7569 ×10 4 g·mol -1 The relative molecular mass distribution was 1.9815.
Application example 20
The linear magnetic tetranuclear nickel complex prepared in the example 1 is taken as a catalyst 19mg, a cocatalyst AIBN 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is performed firstly, nitrogen is then filled, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are injected by a syringe with scales after three times of circulation, and finally rubber tubes on two sides are clamped by hemostatic forceps. And (3) carrying out reaction for 0.5h in an electric heating sleeve at 90 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after the completion of the reaction, and then adding 50mL of ethanol for standing. Filtering the obtained precipitate PMMA, washing with ethanol for multiple times, and vacuum drying to constant weight. The activity is 0.0064 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight of 0.0067X 10 4 g·mol -1 The relative molecular mass distribution was 1.2537.
Application example 21
The linear magnetic tetranuclear nickel complex prepared in the example 1 is taken as a catalyst 19mg, a cocatalyst AIBN 20mg and a rotor are added into a dried three-neck flask, the upper mouth of the three-neck flask is sealed, the other two mouths are respectively connected with a vacuum pump and a nitrogen bag by a rubber tube, vacuum pumping is performed firstly, nitrogen is then filled, a certain amount of MMA (2 mL) and toluene (5 mL) which are dried are injected by a syringe with scales after three times of circulation, and finally rubber tubes on two sides are clamped by hemostatic forceps. And (3) carrying out reaction for 0.5h in an electrothermal sleeve at 80 ℃, adding 1-2mL of 5% acid ethanol serving as a terminator after finishing the reaction, and then adding 50mL of ethanol for standing. The obtained precipitate PMMA is filtered, washed by ethanol for multiple times and dried in vacuum until the weight is constant. The activity is 1.8786 multiplied by 10 4 g·mol -1 ·h -1 Molecular weight 1.8244 ×10 4 g·mol -1 The relative molecular mass distribution was 5.0541.
In the embodiment, the linear magnetic tetranuclear nickel complex has good molecular structure stability and high catalytic performance, and can be used as a catalyst to quickly and efficiently catalyze MMA to polymerize into PMMA in a short time.
The polymerization of MMA with the linear magnetic tetranuclear nickel complexes according to the invention was investigated at different polymerization temperatures (Tp). The linear magnetic tetranuclear nickel complex reaches the highest activity 4.8924 multiplied by 10 at 100 DEG C 4 g·mol -1 ·h -1 . As Tp increases or decreases, the activity value decreases relative to 100 ℃. This shows that the linear magnetic tetranuclear nickel complex can be used as a nickel catalyst to catalyze the polymerization of MMA at higher temperature. Time has a significant effect on the catalytic activity of MMA polymerization. When the polymerization time was 0.5h, the activity of the catalyst was the highest, reaching 4.8924 ×10 4 g·mol -1 ·h -1 Realizes the polymerization of MMA in a short time, achieves the purpose of high speed and high efficiency, and solves the problems of long time and low catalyst activity.
Thus, the catalyst was at 0.5 hoursThe maximum catalytic activity for MMA polymerization at 100 ℃ can reach 4.8924 multiplied by 10 4 g·mol -1 ·h -1 。
The foregoing description of the preferred embodiment of the invention is not intended to limit the invention, but rather to enable any modification, equivalent replacement, improvement or the like to be made without departing from the spirit and principles of the invention, and is intended to be included within the scope of the present invention.
In conclusion, the linear magnetic tetranuclear nickel complex is a linear multifunctional magnetic nickel complex with a chemical general formula of { [ Ni ] 4 L 2 (H 2 O) 3 CH 3 OH]·2CH 3 OH·2CH 3 CN·2H 2 O，H 2 L＝C 19 H 20 N 4 O 5 -a }; wherein the linear magnetic tetranuclear nickel complex belongs to monoclinic system and P2 1 N space group whose unit cell parameter is axial lengthThe axis angle α=90°, β= 111.8860 (10) °, γ=90°, the unit cell volume is +.>Dc＝1.601g/cm 3 ，Z＝4，F(000)＝2552.0，μ(MoKa)＝0.71073，GooF＝1.067，R 1 ＝0.0735，wR 2 The crystal size was 0.2mm×0.12mm×0.1mm = 0.1768. />
The invention provides a novel-structure multifunctional linear magnetic tetranuclear nickel complex catalyst, which has good catalytic activity and application value in catalyzing carbon dioxide to generate cyclic carbonate and catalyzing Methyl Methacrylate (MMA) polymerization. Compared with the prior art, the linear magnetic tetranuclear nickel complex catalyst provided by the invention does not contain noble metal, is easy to obtain in raw materials, simple in preparation process, less in time consumption, mild in reaction condition, high in yield and wide in industrial application prospect when being used for synthesizing cyclic carbonate and polymerizing methyl methacrylate.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (9)

1. The linear magnetic tetranuclear nickel complex is characterized by comprising the following structural formula:
。
2. the method for preparing a linear magnetic tetranuclear nickel complex according to claim 1, comprising the steps of:
uniformly dispersing the ligand in a reaction solvent, continuously adding nickel salt for carrying out a coordination reaction after deprotonation treatment to obtain a solution mixed system, filtering the obtained solution mixed system to obtain filtrate, and drying the obtained filtrate to obtain the linear magnetic tetranuclear nickel complex;
wherein the ligand has the following structural formula:
。
3. the method for preparing a linear magnetic tetranuclear nickel complex according to claim 2, wherein the mass ratio of the ligand to the nickel salt is 1: 1-1: 2.
4. the preparation method of the linear magnetic tetranuclear nickel complex according to claim 2, wherein the reaction solvent is a mixed solution composed of acetonitrile and methanol, and the mixed volume ratio of acetonitrile to methanol is 1: 1-1: 6.
5. the method for preparing a linear magnetic tetranuclear nickel complex according to claim 2, wherein the nickel salt is one or more of nickel chloride, nickel acetate, nickel nitrate and nickel sulfate.
6. The method for preparing a linear magnetic tetranuclear nickel complex according to claim 2, wherein the temperature of the coordination reaction is 15-35 ℃ and the time is 15-30 min.
7. The method for preparing a linear magnetic tetranuclear nickel complex according to claim 2, wherein the drying process comprises: naturally volatilizing for 7-14 days or drying for 30-40 h at 60-70 ℃ in a high-temperature oven.
8. The method for preparing a linear magnetic tetranuclear nickel complex according to claim 2, wherein the alkali used for deprotonation is one or two of sodium hydroxide, triethylamine, potassium hydroxide and lithium hydroxide.
9. The use of a linear magnetic tetranuclear nickel complex according to claim 1 for catalyzing carbon dioxide to form cyclic carbonates and for catalyzing methyl methacrylate polymerization.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108772102A (en) * 2018-04-16 2018-11-09 兰州大学 Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108772102A (en) * 2018-04-16 2018-11-09 兰州大学 Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester

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Title
Li Wang et al.."A linear tetranuclear Ni(II) acyl hydrazone Schiff base complex:preparation, crystal structure and catalytic application ".《Transition Metal Chemistry》.2022,第47卷第275-281页. *

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