Chiral [Cu (DPEN) 2] Ti4L6 crystalline substance and preparation method thereof

Abstract

The invention provides a chiral [Cu (DPEN) 2] amp; the invention discloses a Ti4L6 crystalline substance and a preparation method thereof. The chiral [Cu (S-DPEN) 2] amp is synthesized by inducing and splitting a Ti4L6 cage by using a chiral Cu unit formed by chiral ligand DPEN and Cu < 2 + > ions in situ; [delta delta delta delta delta-Ti4L6] and [Cu (R-DPEN) 2] amp; and [lambda lambda lambda lambda lambda-Ti4L6] is a crystalline substance. The chiral [Cu (S-DPEN) 2] amp is prepared; [delta delta delta delta delta-Ti4L6] and [Cu (R-DPEN) 2] amp; the [Lambda Lambda Lambda Lambda-Ti4L6] crystalline substance as a precursor can be assembled with various metal ions and organic auxiliary ligands to prepare a chiral Ti4L6 cage-based crystalline material.

Description

Technical Field

[0001] The present invention belongs to the technical field of crystal material preparation, and in particular relates to a chiral [Cu(DPEN)2]&Ti4L6 crystalline material and a preparation method thereof. Background Art

[0002] Over the past few decades, scientists have constructed numerous metal-organic cages (MOCs) with various geometric configurations. Tetrahedral cages (M4L4 and M4L6) have been the most studied. Most M4L6 tetrahedral cages are chiral, but two configurations exist simultaneously: ΔΔΔΔ-M4L6 and ΛΛΛΛ-M4L6. To date, only a few M4L6 cages have been induced to resolve using chiral organic molecules. Ti4L6 tetrahedral cages constructed with pamoic acid (L) ligands also exist in two configurations: ΔΔΔΔ-[Ti4L6] and ΛΛΛΛ-[Ti4L6]. Ti4L6 cages exhibit high solubility, stability, and abundant coordination sites. Various Ti4L6 cage-based functional materials have been successfully synthesized via a two-step reaction. However, the assembly of chiral Ti4L6 cage-based materials has been slow to progress. In order to realize its chiral assembly application, the Ti4L6 cage needs to be chirally split first to obtain a single-configuration Ti4L6 cage. Summary of the Invention

[0003] In order to achieve the above-mentioned object, the present invention first provides a chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material;

[0004] Wherein, L is pamoic acid; S-DPEN is (1S,2S)-1,2-diphenylethylenediamine; R-DPEN is (1R,2R)-1,2-diphenylethylenediamine;

[0005] The chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] crystal is a eutectic formed by one [ΔΔΔΔ-Ti4L6] cage, four [Cu(S-DPEN)2](H2O)2] cation units, and four H2O molecules;

[0006] The chiral [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material is a eutectic formed by one [ΛΛΛΛ-Ti4L6] cage, four [Cu(R-DPEN)2](H2O)2] cation units and four H2O molecules;

[0007] The chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material has substantially Figure 2 The X-ray powder diffraction pattern is shown.

[0008] According to an embodiment of the present invention, the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material has the following characteristics: Figure 3 Circular dichroism (CD) spectrum shown.

[0009] According to an embodiment of the present invention, the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material has the following characteristics: Figure 4 The crystal morphology shown.

[0010] According to an embodiment of the present invention, through single crystal X-ray analysis, the chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline materials have the following crystal parameters:

[0011]

[0012] According to the present invention, the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline substances are dark red rod-shaped crystalline substances.

[0013] The present invention also provides a method for preparing the chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline material, which is a solvothermal method and comprises the following steps:

[0014] Ti4L6, a metallic copper salt, (1S,2S)-1,2-diphenylethylenediamine or (1R,2R)-1,2-diphenylethylenediamine are heated in a solvent for reaction; when (1S,2S)-1,2-diphenylethylenediamine is used, [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] crystalline substances are obtained; when (1R,2R)-1,2-diphenylethylenediamine is used, [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline substances are obtained;

[0015] Wherein, L is pamoic acid.

[0016] According to the present invention, the Ti4L6 is a molecular cage, and its preparation process can refer to the method described in patent document CN 109678702CA.

[0017] According to the present invention, the method includes the following steps: mixing Ti4L6, metal copper salt, (1S,2S)-1,2-diphenylethylenediamine or (1R,2R)-1,2-diphenylethylenediamine and a solvent, stirring, placing in a glass bottle or a polytetrafluoroethylene pressure container, reacting at 60-160°C, and then naturally cooling to room temperature.

[0018] According to an embodiment of the present invention, the metal copper salt of the present invention is one or a mixture of two or more of copper acetate, copper sulfate, cuprous iodide, cuprous oxide, etc., preferably cuprous oxide or copper acetate.

[0019] According to an embodiment of the present invention, the molar ratio of Ti4L6 to the metal copper salt can be (0.1:1) to (5:1), for example, (0.1:1) to (3:1), such as (0.15:1) to (0.8:1).

[0020] According to an embodiment of the present invention, the molar ratio of Ti4L6 to (1S,2S)-1,2-diphenylethylenediamine or (1R,2R)-1,2-diphenylethylenediamine can be (0.05:1) to (1:1), preferably (0.2:1) to (0.5:1).

[0021] According to the present invention, the solvent is a mixture of an amide solvent, an alcohol solvent and water (eg, deionized water).

[0022] According to the present invention, the amide solvent is selected from one or a mixture of two or more of formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, polyacrylamide, caprolactam, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-diethylformamide, preferably N,N-dimethylformamide or N,N-dimethylacetamide.

[0023] According to the present invention, the alcoholic solvent is selected from the alcohol containing 1-40 carbon atoms (for example 1-30 carbon atoms, 1-20 carbon atoms, 1-10 carbon atoms, 1-6 carbon atoms) or the mixture of alcohols, for example, selected from methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isopropylcarbinol, the tert-butyl alcohol, n-amyl alcohol, isopentanol, neopentyl alcohol, n-hexanol, cyclohexanol or any two or more mixtures thereof. As an example, the alcoholic solvent can be selected from ethanol, isopropyl alcohol, n-propyl alcohol, the tert-butyl alcohol, n-butanol, isopropylcarbinol or any two or more mixtures thereof, and is preferably n-propyl alcohol or ethanol.

[0024] According to an embodiment of the present invention, the solvent is a mixture of N,N-dimethylformamide, ethanol and distilled water, and the volume ratio of the three is (2-5):(1-3):1, for example, 3:2:1.

[0025] According to the present invention, the reaction temperature may be 60-160°C; preferably 60-120°C, such as 80°C.

[0026] According to the present invention, the reaction time can be 24 to 240 hours, preferably 48 to 150 hours, such as 72 hours. Specifically, the reaction can be carried out at 80° C. for 72 hours, or at 100° C. for 48 hours.

[0027] According to the present invention, the solvent reaction can be carried out in a glass bottle or a polytetrafluoroethylene pressure container; preferably, it is carried out in a glass bottle.

[0028] According to the present invention, the solid phase (i.e., crystalline substance) separated in step (2) is cleaned, and it is further preferred to use alcohol to clean the separated solid phase. The alcohol solvent used for cleaning may be the same as or different from the alcohol solvent added in the reaction stage. The mixture is then dried at room temperature to obtain chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline substances.

[0029] According to the present invention, the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline materials are easily soluble in amide solvents.

[0030] The present invention also provides the use of the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline materials as precursors for molecular assembly with other metal ions to prepare chiral Ti4L6 cage-based crystalline materials.

[0031] Beneficial effects

[0032] The inventors used a chiral ligand DPEN and Cu 2+ The chiral Cu unit formed in situ by ions induces the splitting of the Ti4L6 cage and then synthesizes chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline substances. The prepared chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline substances can be assembled with various metal ions and organic auxiliary ligands as precursors to prepare chiral Ti4L6 cage-based crystalline materials. The raw materials of the splitting process of the present invention are easy to obtain and low in price, the synthesis steps are simple and convenient for large-scale production, and the post-processing is simple and easy. The pure phase crystalline product can be obtained by simple alcohol washing and separation and drying at room temperature, which has certain application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Schematic diagram for the preparation of chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline materials;

[0034] Figure 2 X-ray powder diffraction patterns of the chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline materials prepared in Example 1;

[0035] Figure 3 Circular dichroism (CD) spectra of the chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline materials prepared in Example 1;

[0036] Figure 4 These are single crystal photos of the chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline materials prepared in Example 1. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the scope of protection of the present invention.

[0038] Unless otherwise stated, the reagents used in the present invention are commercially available.

[0039] The single crystal structure analysis of the present invention was performed using a Supernova single crystal diffractometer manufactured by Rigaku Corporation.

[0040] The X-ray powder diffraction test used Cu-Kα radiation as the radiation source.

[0041] Example 1

[0042] Red (Ti4L6) crystals (80 mg, 0.032 mmol), Cu2O (30 mg, 0.21 mmol), (1S,2S)-1,2-diphenylethylenediamine (30 mg, 0.14 mmol), N,N-dimethylformamide (3 mL), ethanol (2 mL) and distilled water (1 mL) were placed in a 20 mL glass bottle, mixed evenly at room temperature, and placed in an oven at 80 ° C for constant temperature reaction for 3 days. The product was taken out, the solid phase was separated, and the solid phase was rinsed with ethanol to obtain dark red rod-shaped chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] crystals.

[0043] By replacing (1S,2S)-1,2-diphenylethylenediamine in the above scheme with (1R,2R)-1,2-diphenylethylenediamine, using the same operation method and reacting under the same conditions, chiral [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline materials can be obtained.

[0044] After testing, the yield of the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline materials prepared in Example 1 can reach more than 40%.

[0045] The crystal parameters of the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline materials prepared in Example 1 are specifically shown in Table 1.

[0046] Table 1

[0047]

[0048] The structural characterization data of the product in Example 1 are shown in Figure 1-4 .

[0049] through Figure 1 and 2 The characterization data confirm that the chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] crystalline material is a eutectic formed by one [ΔΔΔΔ-Ti4L6] cage, four [Cu(S-DPEN)2](H2O)2] cation units and four H2O molecules.

[0050] The chiral [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material is a eutectic formed by one [ΛΛΛΛ-Ti4L6] cage, four [Cu(R-DPEN)2](H2O)2] cation units and four H2O molecules.

[0051] It will be easily understood by those skilled in the art that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. Chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline materials; in, L is pamoic acid; S-DPEN is (1S,2S)-1,2-diphenylethylenediamine; R-DPEN is (1R,2R)-1,2-diphenylethylenediamine; The chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] crystal is a eutectic formed by one [ΔΔΔΔ-Ti4L6] cage, four [Cu(S-DPEN)2](H2O)2] cation units, and four H2O molecules; The chiral [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material is a eutectic formed by one [ΛΛΛΛ-Ti4L6] cage, four [Cu(R-DPEN)2](H2O)2] cation units and four H2O molecules; The chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material has an X-ray powder diffraction pattern substantially as shown in FIG2.

2. The chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline material according to claim 1, characterized in that It has a circular dichroism (CD) spectrum as shown in FIG3 .

3. The chiral [Cu(S-DPEN)2]&[ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2]&[ΛΛΛΛ-Ti4L6] crystalline material according to claim 1 or 2, characterized in that It has a circular dichroism (CD) spectrum as shown in FIG3 .

4. The chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline material according to any one of claims 1 to 3, characterized in that It has a crystal morphology as shown in FIG4 .

5. The chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline material according to any one of claims 1 to 4, characterized in that It has the following crystal parameters:

6. The method for preparing the chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] or [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline material according to any one of claims 1 to 5 is a solvothermal method, characterized in that: The following steps are involved: Ti4L6, a metallic copper salt, (1S,2S)-1,2-diphenylethylenediamine or (1R,2R)-1,2-diphenylethylenediamine are heated in a solvent for reaction; when (1S,2S)-1,2-diphenylethylenediamine is used, [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] crystalline substances are obtained; when (1R,2R)-1,2-diphenylethylenediamine is used, [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline substances are obtained; Wherein, L is pamoic acid.

7. The method according to claim 6, characterized in that The method comprises the following steps: mixing Ti4L6, a metal copper salt, (1S,2S)-1,2-diphenylethylenediamine or (1R,2R)-1,2-diphenylethylenediamine and a solvent, stirring the mixture, placing the mixture in a glass bottle or a polytetrafluoroethylene pressure vessel, reacting the mixture at 60-160° C., and then naturally cooling the mixture to room temperature.

8. The method according to claim 6 or 7, characterized in that The metal copper salt is one or a mixture of two or more of copper acetate, copper sulfate, cuprous iodide and cuprous oxide.

9. The method according to any one of claims 6 to 8, characterized in that: The molar ratio of the Ti4L6 to the metal copper salt is (0.1:1) to (5:1). Preferably, the molar ratio of Ti4L6 to (1S,2S)-1,2-diphenylethylenediamine or (1R,2R)-1,2-diphenylethylenediamine is (0.05:1) to (1:1). Preferably, the solvent is a mixture of an amide solvent, an alcohol solvent and water. Preferably, the solvent is a mixture of N,N-dimethylformamide, ethanol and distilled water, and the volume ratio of the three is (2-5):(1-3):

1. Preferably, the reaction temperature is 60-160°C.

10. Use of the chiral [Cu(S-DPEN)2] & [ΔΔΔΔ-Ti4L6] and [Cu(R-DPEN)2] & [ΛΛΛΛ-Ti4L6] crystalline materials according to any one of claims 1 to 5 as precursors for molecular assembly with other metal ions to prepare chiral Ti4L6 cage-based crystalline materials.

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