KR20140098948A - Zn(ii) coordination polymers constructed by malonate and bipyridyl ligands, photoluminescence and catalyst for transesterification comprising the same - Google Patents

Abstract

The present invention relates to a crystal structure, fluorescence characteristics, and characteristics as a catalyst for transesterification of coordination polymers composed of zinc, malonate, and bipyridyl ligands. The coordination polymers of the present invention can be used as a fluorescent material and a display device for electronic products and the like. In addition, the coordination polymers of the present invention can perform the role of a transesterification catalyst which can efficiently and easily be reused at mild conditions.

Description

(II) complexes composed of malonic acid and bipyridyl ligands, fluorescent dyes containing the same and ester exchange reaction catalysts (Zn (Ⅱ) coordination structures constructed by malonate and bipyridyl ligands, photoluminescence and catalyst for transesterification comprising the same)

The present invention relates to zinc (II) complexes composed of malonic acid and bipyridyl ligands, fluorescent dyes containing the same, and ester exchange reaction catalysts.

Metal-organic frameworks (MOF) are valuable materials for a wide range of applications such as selective gas adsorption, heterogeneous catalysis, separation, drug delivery, and biological imaging. These metal-organic structures have consisted of ligands comprising a metal and a carboxy group. Dicarboxylic acids have provided a variety of metal ions and various metal-organic structures, and their structures exhibit various dimensional properties due to different coordination and pore sizes. Rigid aromatic dicarboxylic acids or flexible cyclohexane dicarboxylic acids have already been selected as dicarboxylic acid ligands of coordination polymers.

Recently, we have disclosed two metal-organic structures using copper and flexible glutaric acid and bipyridyl ligands. These metal-organic structures have similar pore shapes and different pore dimensions. In addition, it exhibits carbon dioxide selectivity to nitrogen and hydrogen as a heterogeneous catalyst for efficient and easy reusable ester exchange reaction.

In addition, since it has fluorescence properties, it can be applied to a variety of applications such as a chemical sensor and an electroluminescent display device.

 Bifunctional 3D Cu-MOFs containing glutarates and bipyridyl ligands: selective CO2 sorption and heterogeneous catalysis (Dalton Transactions, 2012, 41, 12759-12765)

The present invention provides a novel complex composed of zinc and malonic acid and bipyridyl ligands, clarifies the crystal structure of the complex by X-ray analysis, and reveals the fluorescence property of the complex and the characteristics of the ester exchange reaction catalyst The purpose.

In order to achieve the above object, the present invention provides a complex composed of zinc and malonic acid and a bipyridyl ligand represented by the general formulas (1) to (4).

[Chemical Formula 1]

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-4,4'-bpy)] (H ₂ O) (CH ₃ CN)

(2)

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpa)] (H ₂ O) (CH ₃ CN)

(3)

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpe)] (H ₂ O) (CH ₃ CN)

[Chemical Formula 4]

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpp)] (H ₂ O) (CH ₃ CN)

Wherein bpy is 4,4'-bipyridine, bpa is 1,2-bis (4-pyridyl) ethane, bpe is trans-1,2-bis (4pyridyl) 3-bis (4-pyridyl) propane.

The present invention also provides a fluorescent dye comprising at least one complex selected from the group consisting of the complexes of the above formulas (2) to (3).

The present invention also provides a display device comprising the fluorescent dye.

The present invention also provides a reusable ester exchange reaction catalyst comprising at least one complex selected from the group consisting of the complexes of formulas (1) to (4).

The present invention provides complexes composed of zinc and malonic acid and bipyridyl ligands.

The complex compound of the present invention can be used as a fluorescent material and can be used as a display device for electronic products and the like.

In addition, the complex of the present invention can serve as an efficient and easily reusable ester exchange reaction catalyst under mild conditions.

1 (a) is an X-ray crystal structure ( a axis) of Formula 1 and (b) is an X-ray crystal structure ( b axis) of Formula 1. FIG. Solvent molecules were omitted from the figure to observe the clear structure.
2 (a) is an X-ray crystal structure ( a axis) of Formula 2 and (b) is an X-ray crystal structure ( c axis, two-dimensional sheet) of Formula 2. FIG. Solvent molecules were omitted from the figure to observe the clear structure.
FIG. 3 (a) is an X-ray crystal structure ( c- axis) of Formula 3 and (b) is an X-ray crystal structure of Formula 3 ( a- axis, two-dimensional sheet). Solvent molecules were omitted from the figure to observe the clear structure.
4 (a) is an X-ray crystal structure ( c- axis) of Formula 4, and (b) is an X-ray crystal structure of Formula 4 ( b- axis, two-dimensional sheet). Solvent molecules were omitted from the figure to observe the clear structure.
5 is a schematic representation of the structure in which the carboxylate of malonic acid is bonded to the complexes of formulas 1-4.
6 (a) is a one-dimensional channel of the formula (1), (b) is a one-dimensional channel of the formula (2), (c) is a one-dimensional channel of the formula (3), and (d) is a one-dimensional channel of the formula (4).
FIG. 7 is a graph showing the fluorescence spectra of bipyridyl ligands and malonic acid used in the complexes of formulas (2) and (3) in the solid state.

Hereinafter, the present invention will be described in more detail.

The present invention provides complexes composed of zinc and malonic acid and bipyridyl ligands represented by the general formulas (1) to (4).

[Chemical Formula 1]

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-4,4'-bpy)] (H ₂ O) (CH ₃ CN)

(2)

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpa)] (H ₂ O) (CH ₃ CN)

(3)

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpe)] (H ₂ O) (CH ₃ CN)

[Chemical Formula 4]

[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpp)] (H ₂ O) (CH ₃ CN)

Wherein bpy is 4,4'-bipyridine, bpa is 1,2-bis (4-pyridyl) ethane, bpe is trans-1,2-bis (4pyridyl) 3-bis (4-pyridyl) propane.

The X-ray structure analysis results of the complexes of the above formula show that all of them are three-dimensional structures of general [{Zn (H ₂ O) (μ-malonate)} ₂ (μ-bipyridyl)]. Malonate is bridged with zinc ions to form a two-dimensional layer, and bipyridyl ligands (4,4'-bpy, bpa, bpe, bpp) act as pillars to form a three-dimensional structure. The longer the length of the ligand that acts as a column, the larger the volume of the vacancy.

The present invention also provides a fluorescent dye comprising at least one complex selected from the group consisting of the complexes of the above formulas (2) to (3).

The compound of the present invention emits light at? = 340 nm to? = 370 nm. Such a compound of the present invention can be used as a material representing a color of a display device.

That is, the present invention provides a display device comprising the fluorescent dye.

The present invention also provides a reusable ester exchange reaction catalyst comprising at least one complex selected from the group consisting of the complexes of formulas (1) to (4). The above ester exchange reaction catalyst is reusable and provides a possibility of being used as an environmentally friendly catalyst. The ester exchange reaction is preferably carried out at a temperature of 40 캜 to 60 캜, and more preferably 45 캜 to 55 캜.

Hereinafter, the present invention will be described in detail with reference to examples.

However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

Example 1. Preparation of a complex of {{Zn ( H ₂ O ) ( μ- malonate )} ₂ ( μ- 4,4'- bpy )] ( H ₂ O ) ( CH ₃ CN )

(13.1 mg, 0.125 mmol) of malonic acid and 37.9 mg (0.125 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O were dissolved in 4 mL of water and then 39.8 mg (0.25 mmol) of 4,4'- mL < / RTI > acetonitrile solution. 54.3 mg of Compound (1) was obtained, and the crystal structure of the complex was analyzed by X-ray analysis. The crystal structure is shown in Fig.

IR measurement results as described below were obtained.

v (cm ^-1 ) = 1563 (s), 1446 (m), 1347 (s), 1218 (w), 1074 (w), 870 (w), 813 (m), 698 ).

The results of the elemental analysis of the formula 1 C ₁₈ H ₂₁ N ₃ O ₁₁ Zn ₂ (molecular weight 586.12) were as follows.

Theoretical values: C, 36.88; H, 3.62; N, 7.17%

Experimental value: C, 36.35; H, 3.56; N, 6.93%

As a result of the elemental analysis, the difference between the theoretical value and the experimental value of Chemical Formula 1 was insignificant. Thus, it can be seen that the compound of formula 1 was prepared as a result of this experiment.

Example 2. Preparation of complexes of [{Zn ( H ₂ O ) ( μ- malonate )} ₂ ( μ- bpa )] ( H ₂ O ) ( CH ₃ CN )

13.1 mg (0.125 mmol) of malonic acid and 37.9 mg (0.125 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O were dissolved in 4 mL of water and then 47.5 mg (0.25 mmol) of 1,2- mmol) was dissolved in 4 mL of acetonitrile solution. 26.7 mg of the compound of Formula 2 was obtained, and the crystal structure of the complex was analyzed by X-ray analysis. The crystal structure is shown in FIG. 2 below.

IR measurement results as described below were obtained.

v (cm ^-1 ) = 1557 (s), 1444 (m), 1337 (s), 1224 (w), 1022 (w), 873 (w), 826 (m), 694 ), 543 (m).

The results of elemental analysis of the formula 2 C ₁₁ H ₁₃ N ₂ O ₅ Zn (molecular weight 318.60) were as follows.

Theoretical values: C, 41.47; H, 4.12; N, 8.79%

Found: C, 41.89; H, 4.13; N, 9.02%

In the above elemental analysis, the difference between the theoretical value and the experimental value of the formula (2) was insignificant. Thus, it can be seen that the formula 2 was prepared as a result of this experiment.

Example 3. Preparation of complexes of [{Zn ( H ₂ O ) ( μ- malonate )} ₂ ( μ- bpe )] ( H ₂ O ) ( CH ₃ CN )

13.1 mg (0.125 mmol) of malonic acid and 37.9 mg (0.125 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O were dissolved in 4 mL of water, and then 47.0 mg of trans-1,2-bis (4- pyridyl) (0.25 mmol) was dissolved in 4 mL of acetonitrile solution. 28.6 mg of Formula 3 was obtained and the crystal structure of the complex was analyzed by X-ray analysis. The crystal structure is shown in FIG. 3 below.

IR measurement results as described below were obtained.

v (cm ^-1 ) = 1571 (s), 1443 (m), 1345 (s), 1224 (w), 1022 (w), 979 ), 550 (m).

The results of elemental analysis of the formula 3 C ₁₁ H ₁₂ N ₂ O ₅ Zn (molecular weight 317.6) were as follows.

Theoretical values: C, 41.60; H, 3.82; N, 8.82%

Found: C, 42.05; H, 3.75; N, 8.53%

In the elemental analysis, the difference between the theoretical value and the experimental value of the formula (3) was insignificant. Therefore, it can be seen that Formula 3 was prepared as a result of this experiment.

Example 4. Preparation of complexes of Zn ( H ₂ O ) ( μ- malonate )} ₂ ( μ- bpp )] ( H ₂ O ) ( CH ₃ CN )

13.1 mg (0.125 mmol) of malonic acid and 37.9 mg (0.125 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O were dissolved in 4 mL of water, and 50.6 mg (0.25 mmol) of 4,4'-trimethylenedipyridine Was slowly added over 4 mL of acetonitrile solution. 67.2 mg of the compound of Formula 4 was obtained, and the crystal structure of the complex was analyzed by X-ray analysis. 4 shows the crystal structure.

IR measurement results as described below were obtained.

v (cm ^-1 ) = 1575 (s), 1447 (m), 1339 (s), 1223 (w), 1024 (w), 869 (w), 809 (m), 695 ).

The results of elemental analysis of the formula 4 C ₂₃ H ₂₈ N ₄ O ₁₀ Zn ₂ (molecular weight 651.23) were as follows.

Theoretical values: C, 42.42; H, 4.34; N, 8.61%

Found: C, 41.88; H, 4.30; N, 8.72%

In the above elemental analysis, the difference between the theoretical value and the experimental value of the formula (4) was insignificant. Thus, it can be seen that the formula 4 was prepared as a result of this experiment.

Experimental Example  One. Example  1 to 4 complex Thermal weight  analysis

The thermal stability of the complexes of Examples 1 to 4 was measured using TGA.

In the TGA curve of the complex of Example 1, the loss of one acetonitrile molecule (theoretical value: 7.00%) of 7.25% at 45 ° C to 83 ° C and the loss of three water molecules of 9.50% at 84 ° C to 218 ° C %), The loss of 56.38% malonic acid and 4,4'-bipyridyl ligand (theoretical value 56.00) was observed at 219 ° C to 401 ° C.

In the TGA curve of the complex of Example 2, the loss (theoretical value: 18.54%) of each acetonitrile and water molecule of 18.50% at 26 ° C to 218 ° C, 1, The loss of the malonic acid coupled with the 2-bis (4-pyridyl) ethane ligand (theoretical value 55.92) was observed.

In the TGA curve of the complex of Example 3, the loss of one acetonitrile and water molecule (theoretical value: 18.60%) was 18.50% at 66 ° C to 229 ° C, and the half of 50.63% at 230 ° C to 495 ° C -Bis (4-pyridyl) ethylene ligand bound to malonic acid (theoretical value 50.73) was observed.

In the TGA curve of the complex of Example 4, the loss of two acetonitrile and water molecules (theoretical value: 18.14%) at 18.00% at 26 DEG C to 200 DEG C and one 47.48% (Theoretical value 51.95) of two molecules of malonic acid bound to the bipyridyl ligand was observed.

Therefore, it was found that the complexes of Examples 1 to 4 were thermally stable.

Experimental Example  2. Example  1 to Example  Fluorescence analysis of complexes of 4

The complexes and bipyridyl ligands of Examples 1 to 4 were measured for fluorescence in a solid state at room temperature.

The fluorescence emission of the complexes of Examples 1 to 4 was not measured in the complexes of Example 1 and Example 4 under the same experimental conditions. (Λ _ex = 329 nm) in Example 2, λ = 363 nm (λ _ex = 328 nm) in Example 3 and λ = 445-470 nm (λ _ex = 229 nm) , bpe ligand at λ = 510 nm (λ _ex = 452 nm) and malonic acid at λ = 455-490 nm (λ _ex = 320 nm).

As shown in FIG. 7, the emission bands of the complexes of Example 2 and Example 3 were shifted to blue relative to the respective ligands. It is considered that the emission peak of the complexes of Example 2 and Example 3 is due to metal-to-ligand charge transfer (MLCT).

At room temperature, the complex of Example 2 showed a stronger luminescence than the other complexes, especially the complex of Example 3, because it increases the intensity of the complex and reduces energy loss due to non-radiation damping.

In addition, the strong luminescence of the complex of Example 2, which is in a solid state at room temperature, indicates that it is useful as a mixed inorganic-organic photoactive material.

Experimental Example  3. Example  1 to 4 complex-catalyzed ester exchange reaction

After 0.05 mmol of phenylacetate was dissolved in 1.0 mL of methanol, 5.0 mg of each of the complexes of Examples 1 to 4 (8.5 x 10 ^-3 mmol of Example 1, 8.5 x 10 ^-3 mmol of the complex of Example 2 was 15.7 x 10 ^-3 mmol, Example 3 was 15.7 x 10 ^-3 mmol, and Example 4 was 7.7 x 10 ^-3 mmol).

The reaction solution was periodically analyzed by gas chromatography until the reaction was completed with stirring at 450 rpm at 50 DEG C, and the yield was determined based on the synthesis of methylacetate.

The complexes of Examples 1-4 of the present invention produced methyl acetate quantitatively for 7, 9, 7, and 9 days, respectively. On the other hand, in the absence of the complexes of Examples 1 to 4, ester exchange reaction of phenylacetate and methanol hardly occurred during the same period. Also, the complexes of Examples 1 to 4 were experimentally observed for reusability which can be used several times in the ester exchange reaction. As shown in Table 1, the same efficiencies were exhibited for the same period even when used for ester exchange reactions up to 5 times each.

 [Reaction Scheme 1]

Recycle Example 1
(Period / day) Conversion
(%) Example 2
(Period / day) Conversion
(%) Example 3
(Period / day) Conversion
(%) Example 4
(Period / day) Conversion
(%) One 7 100 9 100 7 100 9 100 2 7 100 9 100 7 100 9 100 3 7 100 9 100 7 100 9 100 4 7 100 9 100 7 100 9 100 5 7 100 9 100 7 100 9 100

Claims (5)

Complexes composed of zinc and malonic acids and bipyridyl ligands represented by the general formulas (1) to (4).
[Chemical Formula 1]
[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-4,4'-bpy)] (H ₂ O) (CH ₃ CN)
(2)
[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpa)] (H ₂ O) (CH ₃ CN)
(3)
[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpe)] (H ₂ O) (CH ₃ CN)
[Chemical Formula 4]
[(Zn (H ₂ O) (μ-malonate)} ₂ (μ-bpp)] (H ₂ O) (CH ₃ CN)
Wherein bpy is 4,4'-bipyridine, bpa is 1,2-bis (4-pyridyl) ethane, bpe is trans-1,2-bis (4pyridyl) 3-bis (4-pyridyl) propane. A fluorescent dye comprising at least one complex selected from the group consisting of the complexes of formulas (2) to (3) of claim 1. A display device comprising the fluorescent dye of claim 2. A reusable ester exchange reaction catalyst comprising at least one complex selected from the group consisting of complexes of formulas (1) to (4) of claim 1. The method of claim 4,
Wherein the ester exchange reaction catalyst undergoes the reaction at a temperature of 45 캜 to 55 캜.

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