WO2019134360A1

WO2019134360A1 - An imide-type compound anionic material having room-temperature ferromagnetism and application thereof

Info

Publication number: WO2019134360A1
Application number: PCT/CN2018/096929
Authority: WO
Inventors: 胡德华; 蒋庆林; 马於光; 赵铎凯; 张弜; 毛忠泉; 姚尧
Original assignee: 华南理工大学
Priority date: 2018-01-05
Filing date: 2018-07-25
Publication date: 2019-07-11

Abstract

An imide-type compound anionic material having room-temperature ferromagnetism and an application thereof, belonging to the technical field of organic magnetic materials. The imide-type compound anionic material is obtained by forming a solution or a suspension of an imide-type compound and then reducing, followed by drying. The anionic material comprises an anion of an imide-type compound represented by one or more of a Formula I or a Formula II. In Formula I or Formula II, n = 1, 2, 3; R₁, R₂ are each independently at least one of H, an amino group, a carboxyl group, a hydroxy group, a hydrazino group, or a pyridyl group; X₁-X₄ are each independently an electron withdrawing group, specifically a H, F, Cl, Br, CN, NO₂ group. The anionic material has a Curie temperature exceeding room temperature, has ferromagnetic properties, and is an organic magnetic material with excellent performance. The anionic material is used for preparing an organic magnetic material and/or an organic magnetic device.

Description

An imide compound anion material with room temperature ferromagnetism and application thereof

Technical field

The invention belongs to the technical field of organic magnetic materials, and in particular relates to an imide compound anion material and application thereof. The imide compound anionic material has room temperature ferromagnetism, is used as an organic magnetic material, and is used for preparing an organic magnetic device.

Background technique

Conventional magnets are usually composed of transition metals with unpaired d or f electrons and their oxides or rare earth elements, and are inorganic magnetic materials. The development of organic magnets has been a hot topic in the fields of physics, chemistry and materials science. The usual organic materials are only s and p electrons, which are generally covalently bonded and do not have unpaired electrons. Therefore, in general, organic materials do not have paramagnetic or ferromagnetic properties. Magnetic properties can also be generated in some organic materials by introducing magnetic metal atoms/ions or generating radicals having a single electron occupying orbital. The organic magnetic compound can be classified into a pure organic magnetic compound and a metal-containing organic magnetic compound depending on whether or not the metal atom or ion is contained in the structure. The so-called pure organic magnetic compound means an organic magnet which does not contain a transition metal or a rare earth element. Although some organic magnets have been developed at present, the existing organic magnets have a ferromagnetic Curie temperature at a low temperature, and the known maximum temperature does not exceed 36K. Although organic magnets with higher Curie temperatures were later found in organic charge transfer salts and metal complexes. But the synthesis of pure organic room temperature magnets that do not contain metals remains a significant challenge.

Summary of the invention

In order to overcome the shortcomings and deficiencies of the prior art, it is an object of the present invention to provide an imide-based compound anionic material. In the present invention, an imide compound is constructed in an anionic state (monovalent anion state and/or divalent anion state), and a high performance pure organic magnetic material can be obtained.

Another object of the present invention is to provide an application of the above-described imide compound anionic material. The imide compound anion material is used as an organic magnetic material. The imide compound anion material of the invention has ferromagnetism, and its Curie temperature exceeds room temperature, and the coercive force reaches about 200 Oe, thereby providing a basis for preparing a high performance pure organic magnetic device. The imide compound anion material of the present invention is used to prepare an organic magnetic device.

The object of the invention is achieved by the following technical solutions:

An imide compound anion material comprising an anion after reduction of an imide compound, wherein the anion is one or more of the following structural formulas;

In formula I or II: n = ₁ , ₂ , 3; R ₁ and R ₂ are each independently H, amino, carboxyl, hydroxy, thiol (NH-NH ₂ ), pyridyl (2-substituted pyridine)

3-substituted pyridine

4-substituted pyridine

At least one

X ₁ -X ₄ are each independently an electron withdrawing group (an electron withdrawing group), specifically a H, F, Cl, Br, CN, NO ₂ group.

The imide compound anion material is obtained by forming an imide compound into a solution or suspension and then reducing, and then drying; the reduction means that the imide group is reduced to an anion;

The imide compound has the following structure:

Wherein: n = ₁ , ₂ , 3; R ₁ and R ₂ are each independently H, amino, carboxyl, hydroxy, fluorenyl (NH-NH ₂ ), pyridyl (2-substituted pyridine)

3-substituted pyridine

4-substituted pyridine

) at least one:

X ₁ -X ₄ are each independently an electron withdrawing group (electron withdrawing group), specifically a group of H, F, Cl, Br, CN, NO ₂ .

The imide compound anion material is obtained by reducing an imide compound in a solvent to obtain an anion compound solution/suspension of an imide compound; and then an imide compound anion solution/suspension Dry.

The imide compound anion solution/suspension is prepared by the following method:

The imide compound is mixed with hydrazine hydrate and reduced to obtain an anionic solution or suspension of the imide compound.

The concentration of the imide compound in hydrazine hydrate is 1 to 50 mg/mL.

The reduction reaction is carried out by heating and/or pressurization.

The heating temperature is 50 to 200 ° C, and the pressure of the pressing is 2 to 32 MPa.

The reduction reaction time is from 10 to 48 hours.

Alternatively, the imide compound anion solution/suspension is prepared by mixing an imide compound with an organic solvent, adding a chemical reducing agent, and reducing the reaction to obtain an anionic solution/suspension.

The reduction reaction temperature is -10 to 160 ° C, the reduction reaction time is 0.1 to 48 h, preferably 5 to 48 h;

The amount of the chemical reducing agent is determined according to the characteristics of the reducing agent. If one equivalent of the reducing agent is capable of changing one equivalent of the imide (imide group in the imide compound) into a divalent anion, the reduction is carried out. The amount of the agent used is 1-10 equivalents; if two equivalents of the reducing agent are required to reduce one equivalent of the imide to the dianion, the amount of the chemical reducing agent is 2 to 10 equivalents.

The concentration of the imide compound in an organic solvent is 1 to 50 mg/mL.

The organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, chloroform, dichloromethane, toluene, chlorobenzene, o-dichlorobenzene. And one or more of ethyl acetate, methanol, acetone, acetonitrile, ethylene glycol dimethyl ether, 1,2-dichloroethane, dioxane, pyridine or 2-methylpyrrolidone.

The chemical reducing agent is at least one of an alkali metal, hydrazine hydrate, sodium dithionite, sodium sulfide, and potassium sulfide. The alkali metal is lithium, sodium, potassium or the like.

Alternatively, the imide compound anion solution/suspension is prepared by mixing an imide compound with an organic solvent, and applying a bias voltage to electrochemically reduce to obtain an anion solution/suspension.

The electrochemical reduction time is from 1 s to 10 min, and the bias voltage is from 0 to -2.5 volts.

The concentration of the imide compound in an organic solvent is 1 to 50 mg/mL.

The imide compound anion material is obtained by drying an imide compound anion solution/suspension. The drying is preferably heat drying.

The imide compound anion material is a film or a powder, and the imide compound anion solution/suspension is processed by a conventional technique, preferably spin coating, brush coating, spray coating, dip coating, A film or powder is formed on the substrate by roll coating, screen printing, printing, or ink jet printing.

The imide compound anion material of the present invention has room temperature ferromagnetism and is used as an organic magnetic material.

An organic magnetic material comprising the above imide compound anionic material.

More preferably, an organic magnetic material is an anionic material of the above imide compound. The imide compound anion material is used to prepare an organic magnetic device.

The anion of the imide compound in the anion compound of the present invention after reduction of the imide compound is a monovalent anion and/or a divalent anion.

The material of the present invention has better performance as an organic magnetic material. The imide material selected by the invention has a large conjugate plane structure, and the ordered inter-molecular packing and the molecular spacing are small, so that the interaction is strong, the radicals are arranged in an orderly manner to form a magnetic moment; and the material molecular structure is four. The presence of electron-withdrawing carbonyl groups enables such molecules to form stable monovalent and divalent anionic forms. By constructing materials, anionic materials with divalent as the main component and free radical anions as a small amount of dopants can be realized. Showing a ferromagnetic sequence close to room temperature, the Curie temperature of ferromagnetic transition (Tc = 400K) is significantly improved compared to the reported organic magnets, and the coercivity at room temperature is close to 200 Oe.

The imide compound has good chemical, thermal and light stability and a large conjugated skeleton, and can be widely used in organic solar cells, electroluminescent devices, field effect transistors, self-assembly and bio-fluorescence detectors. Due to the strong intermolecular interaction, the molecular spacing is small, and the imide compound can achieve ferromagnetic coupling. The invention provides an anion-based compound anion material with room temperature ferromagnetism, and has broad application prospects in pure organic magnetic materials and devices.

Compared with the prior art, the present invention has the following advantages and benefits:

(1) The imide compound of the present invention has ferromagnetism, has a Curie temperature exceeding room temperature, and has a large coercive force, and is a room temperature pure organic magnetic material, and has a broad application prospect;

(2) The invention adopts the solution processing technology, the preparation process is simple, and the production cost is low.

DRAWINGS

1 is a UV-Vis absorption spectrum of a phthalimide anion solution prepared in Example 1;

2 is a UV-Vis absorption spectrum of a phthalimide anion film prepared in Example 1;

3 is a cyclic voltammetry curve of a neutral solution of the phthalimide derivative of Example 2;

4 is a hysteresis loop diagram of a phthalimide anion material prepared in Example 1 on the surface of a high-purity silicon wafer at 300K;

5 is a graph showing the magnetization of the phthalimide anion material prepared in Example 1 as a function of temperature; the upper right graph is a graph obtained by extrapolating the Curie temperature according to the Bloch theorem.

Detailed ways

The present invention will be further described in detail below with reference to the embodiments and drawings, but the embodiments of the present invention are not limited thereto. The imide compound anion material of the present invention contains an anion after reduction of an imide compound, and further contains a cation which competes with an anion.

Example 1

The phthalimide derivative (N,N-dihydro-1,6,7,12-tetrachloro-3,4,9,10-tetracarboxylic acid phthalimide) of the present embodiment has the following structure :

Preparation of phthalimide anion solution: 100 mg of N,N-dihydro-1,6,7,12-tetrachloro-3,4,9,10-tetracarboxylic acid phthalimide (Reference) : J. Org. Chem., 2011, 76, 2386-2407) Add 15 mL of hydrazine hydrate solvent (volume fraction 80%), tighten the lid of the kettle, place in an oven, raise the temperature to 140 ° C, react for 24 hours, and end the reaction. After cooling to room temperature, the reaction vessel was transferred to a nitrogen glove box, the kettle lid was opened, and the mother liquor was filtered through a 0.45 um organic phase filter to obtain a phthalimide anion solution (purine phthalimide dianion solution). The ultraviolet-visible absorption spectrum of the phthalimide anion solution (phthalimide divalent ion solution) prepared in this example is shown in FIG.

Preparation of phthalimide anion material:

(1) The surface of the quartz substrate is cleaned by ultrasonic treatment with acetone, micron-sized semiconductor special detergent, deionized water and isopropanol for 10 minutes, and then placed in a constant temperature oven at 80 ° C for 4 hours to dry for use;

(2) Transfer the clean quartz substrate to the nitrogen glove box and place it horizontally. Drip the appropriate amount of the phthalimide anion solution onto the quartz substrate by pipetting, heat, and keep the temperature at 80. At ° C for 15 minutes, a surface-flattened phthalimide dianion material (phthalimide anion material (film)) having a thickness of 300 nm to 5 μm was obtained. The ultraviolet-visible absorption spectrum of the phthalimide anion material (phthalimide dianion material) prepared in this example is shown in FIG. 2 . The phthalimide anion material prepared in this example is on the surface of a high-purity silicon wafer, and the hysteresis loop of 300K is shown in FIG. 4, the coercive force reaches 188 Oe, and the sample exhibits obvious ferromagnetism. The curve of the magnetization of the phthalimide anion material prepared in this example as a function of temperature is shown in FIG. The curve of magnetization as a function of temperature measured by a phthalimide anion material (material sample) under a magnetic field of 1000 Oe is fitted by Bloch equation (Ms(T)/Ms(0)=1-βT ^1.5 ). The Curie temperature of this material sample is close to 400K. 4 and 5, the present invention successfully obtains a room temperature pure organic ferromagnetic material. The performance test data of the phthalimide anion material of this example is shown in Table 1.

Table 1 Example 1 performance test data of phthalimide anion material

Example 2

The phthalimide derivative (N,N-dihydro-3,4,9,10-tetracarboxylic acid phthalimide) of the present embodiment has the following structure:

Preparation of phthalimide anion solution: N,N-dihydro-3,4,9,10-tetracarboxylic acid phthalimide (100 mg) was added to the reaction vessel, and 15 mL of hydrazine hydrate solvent (volume fraction) was added. 80%), after tightening the lid of the lid, put it in an oven, raise the temperature to 140 ° C, react for 24 hours, cool to room temperature after the reaction is finished, transfer the reactor to a nitrogen glove box, open the lid, and use 0.45um for the mother liquor. The organic phase filter was filtered to obtain a phthalimide anion solution (purine phthalimide dianion solution).

Preparation of phthalimide anion material (phthalimide dianion material): same as the procedure of Example 1.

The Curie temperature of the yttrium imide anion material (PBI material) obtained at a magnetic purity of 300 K on the surface of a high-purity silicon wafer was obtained, and the Curie temperature obtained by curve fitting of the magnetization measured under a magnetic field of 1000 Oe with temperature was measured. Table 2 shows:

Table 2 Example 2 performance test data of phthalimide anion material

The phthalimide derivative (N,N-dihydro-3,4,9,10-tetracarboxylic acid phthalimide) of the present example was formulated into a neutral solution (weighing 1 mg of N, N) - Dihydro-3,4,9,10-tetracarboxylic acid phthalimide was added to 10 mL of dichloromethane solvent, stirred at room temperature for 30 minutes, cooled and allowed to stand, and the supernatant was taken to obtain a neutral solution. The cyclic voltammetry curve of the neutral solution of the phthalimide derivative of the present example is shown in FIG.

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments, and any other changes, modifications, substitutions, and combinations may be made without departing from the spirit and scope of the present invention. And simplifications, all of which are equivalent replacement means, are included in the scope of protection of the present invention.

Claims

An imide compound anion material comprising an anion after reduction of an imide compound, wherein the anion is one or more of the following structural formulas;

In the formula I or II: n = 1 , 2 , 3; R 1 , R 2 are each independently at least one of H, an amino group, a carboxyl group, a hydroxyl group, a thiol group, and a pyridyl group;

X 1 -X 4 are each independently an electron withdrawing group, specifically a H, F, Cl, Br, CN, NO 2 group.
An imide compound anion material characterized in that an imide compound is formed into a solution or a suspension and reduced to obtain an anion compound solution/suspension of an imide compound; The compound is obtained by anionic solution/suspension drying; the reduction means that the imide group is reduced to an anion;

The imide compound has the following structure:

Wherein: n = 1 , 2 , 3; R 1 and R 2 are each independently at least one of H, an amino group, a carboxyl group, a hydroxyl group, a thiol group, and a pyridyl group:

X 1 -X 4 are each independently an electron withdrawing group, specifically a H, F, Cl, Br, CN, NO 2 group.
The imide compound anion material according to claim 2, wherein the anion compound solution/suspension is prepared by the following method:

The imide compound is mixed with hydrazine hydrate and reduced to obtain an anionic solution or suspension of the imide compound.
The imide compound anion material according to claim 3, wherein the concentration of the imide compound in hydrazine hydrate is 1 to 50 mg/mL;

The reduction reaction is carried out by heating and/or pressurization;

The heating temperature is 50 to 200 ° C, and the pressure of the pressurization is 2 to 32 MPa;

The reduction reaction time is from 10 to 48 hours.
The imide compound anion material according to claim 2, wherein the anion compound solution/suspension is prepared by the following method: an imide compound and an organic solvent. Mixing, adding a chemical reducing agent, and reducing the reaction to obtain an anionic solution/suspension.
The imide compound anion material according to claim 5, wherein the reduction reaction temperature is -10 to 160 ° C, and the reduction reaction time is 0.1 h to 48 h;

The concentration of the imide compound in an organic solvent is 1 to 50 mg / mL;

The organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, chloroform, dichloromethane, toluene, chlorobenzene, o-dichlorobenzene. And one or more of ethyl acetate, methanol, acetone, acetonitrile, ethylene glycol dimethyl ether, 1,2-dichloroethane, dioxane, pyridine or 2-methylpyrrolidone;

The chemical reducing agent is at least one of an alkali metal, hydrazine hydrate, sodium dithionite, sodium sulfide, and potassium sulfide.
The imide compound anion material according to claim 2, wherein the anion compound solution/suspension is prepared by the following method: an imide compound and an organic solvent. Mixing, applying a bias voltage by electrochemical reduction, an anionic solution/suspension is obtained.
The imide compound anion material according to claim 7, wherein the electrochemical reduction time is from 1 s to 10 min, and the bias voltage is from 0 to -2.5 volts;

The organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, chloroform, dichloromethane, toluene, chlorobenzene, o-dichlorobenzene. And one or more of ethyl acetate, methanol, acetone, acetonitrile, ethylene glycol dimethyl ether, 1,2-dichloroethane, dioxane, pyridine or 2-methylpyrrolidone;

The concentration of the imide compound in an organic solvent is 1 to 50 mg/mL.
The use of the imide compound anion material according to any one of claims 1 or 2 to 8, characterized in that the imide compound anion material is used for preparing an organic magnetic material and/or an organic magnetic device. .
An organic magnetic material comprising one or more of an anionic material of an imide compound, wherein the anionic material of the imide compound is as defined in any one of claims 1 to 8.