An Anionic Imide Material Having Ferromagnetism At Room Temperature And The Use Thereof

Abstract

The anionic imide material is obtained by preparing a solution or a suspension of an imide compound, then reducing and drying the same; the anionic material comprises anions of an imide compound, the anions being at least one selected from the following formula I or formula II; in formula I or II: n=1, 2, or 3; R.sub.1, R.sub.2 are respectively selected from at least one of H, amino, carboxyl, hydroxy, thiol, and pyridyl groups; X.sub.1-X.sub.4 are respectively an electron withdrawing group, and specifically selected from one of H, F, Cl, Br, CN, and NO.sub.2 groups. The anionic material of the present invention has a Curie temperature larger than room temperature and ferromagnetism, and is an organic magnetic material; it may be used for preparing an organic magnetic material and/or an organic magnetic device.

Claims

1. An anionic imide material, comprising anions of a reduced imide compound, the anions being at least one selected from the following formula I or formula II; where in formula I or II: n=1, 2, or 3; R.sub.1, R.sub.2 are respectively selected from at least one of H, amino, carboxyl, hydroxy, thiol, and pyridyl groups; X.sub.1-X.sub.4 are respectively an electron withdrawing group, and specifically selected from one of H, F, Cl, Br, CN, and NO.sub.2 groups. ##STR00005##

2. An anionic imide material, characterized in that: the anionic imide material is obtained by preparing a solution or a suspension of an imide compound, reducing the same to obtain a solution or a suspension of an anionic imide compound, and then drying the solution or the suspension of the anionic imide compound; said reduction refers to reducing the imide group to an anion; the structure of the imide compound is as follows: ##STR00006## where in the formula: n=1, 2, or 3; R.sub.1, R.sub.2 are respectively selected from at least one of H, amino, carboxyl, hydroxy, thiol, and pyridyl groups; X.sub.1-X.sub.4 are respectively an electron withdrawing group, and specifically selected from one of H, F, Cl, Br, CN, and NO.sub.2 groups.

3. The anionic imide material according to claim 2, characterized in that: the solution or the suspension of the imide compound is prepared by the following method: mixing the imide compound with hydrazine hydrate for reduction to obtain the solution or the suspension of the anionic imide compound.

4. The anionic imide material according to claim 3, characterized in that: the imide compound has a concentration of 1-50 mg/mL in hydrazine hydrate; the reduction is carried out under heating and/or pressurization condition; the heating is carried out under 50-200 C., and the pressurization is carried out under 2-32 MPa; the time of the reduction is 10-48 h.

5. The anionic imide material according to claim 2, characterized in that: the solution or the suspension of the anionic imide compound is obtained by mixing the imide compound with an organic solvent and adding a reducing agent for reduction.

6. The anionic imide material according to claim 5, characterized in that: the reduction is carried out under 10-160 C. for 0.1 h-48 h; the concentration of the imide compound in the organic solvent is 1-50 mg/mL; the organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, chloroform, dichloromethane, toluene, chlorobenzene, o-dichlorobenzene, ethyl acetate, methanol, acetone, acetonitrile, ethylene glycol dimethyl ether, 1,2-dichloroethane, dioxane, pyridine and 2-methylpyrrolidone; the reducing agent is at least one of an alkali metal, hydrazine hydrate, sodium dithionite, sodium sulfide, and potassium sulfide.

7. The anionic imide material according to claim 2, characterized in that: the solution or the suspension of the anionic imide compound is obtained by mixing the imide compound with an organic solvent and applying a bias voltage for electrochemical reduction.

8. The anionic imide material according to claim 7, characterized in that: the electrochemical reduction lasts for 1 s-10 min, and the bias voltage is 0 to 2.5 V; the organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, chloroform, dichloromethane, toluene, chlorobenzene, o-dichlorobenzene, ethyl acetate, methanol, acetone, acetonitrile, ethylene glycol dimethyl ether, 1,2-dichloroethane, dioxane, pyridine and 2-methylpyrrolidone; the concentration of the imide compound in the organic solvent is 1-50 mg/mL.

9. Use of the anionic imide material according to claim 1, characterized in that: the anionic imide material is used for preparing an organic magnetic material and/or an organic magnetic device.

10. An organic magnetic material comprising one or more of the anionic imide material as defined in claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] FIG. 1 is a UV-Vis absorption spectrum of a solution of perylene bisimide anions prepared in Example 1;

[0041] FIG. 2 is a UV-Vis absorption spectrum of a perylene bisimide anion film prepared in Example 1;

[0042] FIG. 3 is a cyclic voltammetry curve of a neutral solution of a perylene bisimide derivative in Example 2;

[0043] FIG. 4 is a hysteresis loop diagram of a perylene bisimide material prepared in Example 1 on the surface of a high-purity silicon wafer at 300 K;

[0044] FIG. 5 is a curve plotting the magnetization of a perylene bisimide imide material prepared in Example 1 against temperature; the upper right graph is obtained by fitting the curve according to the Bloch equation to obtain the Curie temperature.

DETAILED DESCRIPTION OF EMBODIMENTS

[0045] 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 anionic imide material of the present invention contains anions after reduction of an imide compound, and further contains cations which match with the anions.

Example 1

[0046] A perylene bisimide derivative (N,N-dihydro-1,6,7,12-tetrachloro-3,4,9,10-tetracarboxyl perylene bisimide) of the present embodiment has the following structure:

##STR00003##

[0047] Preparation of a solution of perylene bisimide anions: 100 mg of N,N-dihydro-1,6,7,12-tetrachloro-3,4,9,10-tetracarboxyl perylene bisimide (Reference: J. Org. Chem., 2011, 76, 2386-2407) was added to 15 mL of hydrazine hydrate solvent (80% by volume), the lid of the reactor used was tightened, the reactor was placed in an oven, then the temperature was raised to 140 C. to react for 24 h. After the reaction, the mixture was cooled to room temperature, the reactor was transferred to a nitrogen glove box, the lid was opened, and the liquid therein was filtered through a 0.45 um organic phase filter to obtain the solution of perylene bisimide anions (purine solution of perylene bisimide divalent anions). The UV-Vis absorption spectrum of the solution of perylene bisimide anions (solution of perylene bisimide divalent anions) prepared in this example is shown in FIG. 1.

[0048] Preparation of an anionic perylene bisimide material:

[0049] (1) The surface of a quartz substrate was cleaned by ultrasonic treatment with acetone, detergent dedicated for micron-sized semiconductor, deionized water and isopropanol in sequence for 10 minutes, and then the substrate was placed in a constant temperature oven at 80 C. for 4 hours for drying;

[0050] (2) The cleaned quartz substrate was transferred to the nitrogen glove box and placed horizontally. An appropriate amount of the solution of perylene bisimide anions was dripped onto the quartz substrate by pipetting; then it was heated at 80 C. for 15 min to obtain a flattened divalent anionic perylene bisimide material (anionic perylene bisimide material (film)) having a thickness of 300 nm-5 m. The UV-Vis absorption spectrum of the anionic perylene bisimide material (divalent anionic perylene bisimide material) prepared in this example is shown in FIG. 2. The anionic perylene bisimide material prepared in this example exhibits a coercive force of 188 Oe on the surface of a high-purity silicon wafer as shown by the hysteresis loop at 300K in FIG. 4, which indicates obvious ferromagnetism thereof. A curve plotting the magnetization of the anionic perylene bisimide material prepared in this example against temperature is shown in FIG. 5. By fitting the curve plotting the magnetization of the anionic perylene bisimide material (sample) against temperature under 1000 Oe according to the Bloch equation (Ms(T)/Ms(0)=1-bT.sup.1.5), the Curie temperature of the sample is found to be near 400 K. With reference to FIG. 4 and FIG. 5, the present invention successfully obtains a pure organic material ferromagnetic at room temperature. Performance of the anionic perylene bisimide material of this example is shown in Table 1.

TABLE-US-00001 TABLE 1 Performance of the anionic perylene bisimide material of example 1 Coercive force Curie Temperature Sample (Oe) (K) Example 1 188 397

Example 2

[0051] A perylene bisimide derivative (N,N-dihydro-3,4,9,10-tetracarboxyl perylene bisimide) of the present embodiment has the following structure:

##STR00004##

[0052] Preparation of a solution of perylene bisimide anions: 100 mg of N,N-dihydro-3,4,9,10-tetracarboxyl perylene bisimide was added in a reactor, 15 mL of hydrazine hydrate solvent (80% by volume) is further added, the lid of the reactor used was tightened, the reactor was placed in an oven, then the temperature was raised to 140 C. to react for 24 h. After the reaction, the mixture was cooled to room temperature, the reactor was transferred to a nitrogen glove box, the lid was opened, and the liquid therein was filtered through a 0.45 um organic phase filter to obtain the solution of perylene bisimide anions (purine solution of perylene bisimide divalent anions).

[0053] Preparation of an anionic perylene bisimide material (divalent anionic perylene bisimide material):

[0054] The preparation is the same as that of Example 1.

[0055] By fitting a curve plotting the magnetization of the anionic perylene bisimide material (PBI material) against temperature under 1000 Oe, the Curie temperature of the PBI material is obtained and shown in Table 2.

TABLE-US-00002 TABLE 2 Performance of the anionic perylene bisimide material of example 2 Coercive force Curie Temperature Sample (Oe) (K) Example 2 142 283

[0056] The perylene bisimide derivative (N,N-dihydro-3,4,9,10-tetracarboxyl perylene bisimide) of the present example was prepared to be a neutral solution (adding 1 mg of N,N-dihydro-3,4,9,10-tetracarboxyl perylene bisimide to 10 mL of dichloromethane solvent, stirring at room temperature for 30 min, cooling and allowing the solution to stand, wherein the supernatant is the neutral solution). A cyclic voltammetry curve of the neutral solution of the perylene bisimide derivative of the present example is shown in FIG. 3.

[0057] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited thereto, and any other changes, modifications, substitutions, combinations and simplifications made without departing from the spirit and scope of the present invention are equivalent means, and are included in the scope of protection of the present invention.