KR101546570B1 - -- 12-4- Zn coordination polymers constructed from flexible -alkane-dicarboxylate and 12-bis4-pyridylethane ligands carbon dioxide sorption and photoluminescence comprising the same - Google Patents

Abstract

The present invention relates to thermal stability, fluorescence properties and carbon dioxide gas adsorbents of zinc complexes composed of alpha, omega-alkane dicarboxylic acids and 1,2-bis (4-pyridyl) ethane ligands.

Description

Zinc complexes composed of flexible alpha, omega-alkane-dicarboxylic acids and 1,2-bis (4-bipyridyl) ethane ligands, fluorescence properties and carbon dioxide adsorbents comprising the same, ω-alkane-dicarboxylate and 1,2-bis (4-pyridyl) ethane ligands, carbon dioxide sorption and photoluminescence comprising the same}

The present invention relates to a zinc complex comprising a flexible alpha, omega-alkane-dicarboxylic acid and a 1,2-bis (4-bipyridyl) ethane ligand, a fluorescent property comprising the same and a carbon dioxide adsorbent.

Dicarboxylic acids have been used in a variety of metal organic frameworks (MOF), and their structures show different dimensions with different coordination schemes and pore sizes. Metal-organic structures are valuable materials that can be applied to a wide range of applications such as selective gas adsorption, heterogeneous catalysts, separation, drug delivery, and biological imaging. The rigid aromatic dicarboxylic acid or flexible cyclohexane dicarboxylic acid is mainly chosen as the dicarboxylic acid ligand of the coordination polymer. In addition, the rigid alpha, omega-alkane-dicarboxylic acids may be suitable ligands for other shaped coordination polymers.

Recently, two metal-organic structures using copper and flexible glutaric acid and bipyridyl ligands have been published. These metal-organic structures have very similar pore shapes and different pore dimensions and have good selectivity for carbon dioxide in the mixture of nitrogen, hydrogen and carbon dioxide. One of these metal-organic structures is characterized by heterogeneous catalysts in an easily reusable ester exchange reaction.

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

The present invention relates to the synthesis of novel zinc complexes composed of flexible alpha, omega-alkane-dicarboxylic acids and 1,2-bis (4-pyridyl) ethane ligands and is characterized by the structure, thermal stability, fluorescence properties, It is aimed to clarify the characteristics as a sieve.

In order to achieve the above object, the present invention provides a process for the preparation of a compound of formula (I) according to claim 1, wherein the compound is selected from the group consisting of zinc and a flexible alpha, omega-alkane-dicarboxylic acid and 1,2- Thereby providing one complex.

[Chemical Formula 1]

[(Zn (H ₂ O) (μ-succinate) (μ-bpa)] 3 (H ₂ O)}]

(2)

[(Zn (H ₂ O) (μ-fumarate) (μ-bpa)] (H ₂ O)}]

(3)

[{Zn (H ₂ O) (μ-glutarate) (μ-bpa)}]

[Chemical Formula 4]

[{Zn (μ-adipate) (μ-bpa)] (H ₂ O)}]

[Chemical Formula 5]

[{Zn (μ-muconate) ₂ (μ-bpa) ₂ ] .4 (H ₂ O)}]

bpa is 1,2-bis (4-pyridyl) ethane.

The present invention also provides a fluorescent dye comprising at least one complex selected from the group consisting of the above-mentioned formulas (1) to (5).

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

Also, the present invention provides a carbon dioxide adsorbent comprising at least one complex selected from the group consisting of the above formulas (1) to (5).

The present invention can be used as a fluorescent material by synthesizing zinc complex with a flexible alpha, omega-alkane-dicarboxylic acid and 1,2-bis (4-pyridyl) Can be utilized. It can also serve as a carbon dioxide adsorbent.

Of Figure 1 (a) of Example 1 complex of _{[{Zn (H 2 O)} (μ-succinate) (μ-bpa)] · 3 (H 2 O)}] the determination of the structure (a-axis), (b ) Shows the state in which four three-dimensional structures of the complex [{Zn (H ₂ O) (μ-succinate) (μ-bpa)] 3 (H ₂ O)} of Example 1 penetrate each other in different colors And the solvent molecules are omitted from the figure in order to observe the clear structure.
2 (a) shows the crystal structure of the complex [{Zn (H ₂ O) (μ-bumarate) (μ-bpa)]. (H ₂ O)} of Example 2, ([Zn (H ₂ O) (μ-bpa)] · (H ₂ O)] of the complex three-dimensional structure Solvent molecules were omitted from the figure for observation.
FIG. 3 (a) is a graph showing the crystal structure ( a- axis, two-dimensional sheet) of the complex [{Zn (H ₂ O) (μ-glutarate) ([Mu] -glutarate ([mu] -bpa)] of the complex compound [{Zn (H ₂ O) 3] are shown in different colors. In order to observe a clear structure, It is omitted from the figure.
(A) of Example 4 complex [{Zn (μ-adipate) (μ-bpa)] · (H 2 O)}] The crystal structure (a-axis) of the, (b) of Fig. 4 of Example 4 complex [{Zn (μ-adipate) (μ-bpa)] · (H 2 O)}] of the four three-dimensional structure that would indicated by a different color appearance from penetrating each other, of solvent molecules in order to observe a specific structure, It is omitted from the figure.
(A) of Example 5 complex of [{Zn (μ-muconate) 2 (μ-bpa) 2] · 4 (H 2 O)}] the determination of the structure (a-axis), (b) of Figure 5 is carried out The five different three-dimensional structures of the complex [{Zn (μ-muconate) ₂ (μ-bpa) ₂ ] .4 (H ₂ O)} of Example 5 are shown in different colors, Solvent molecules were omitted from the figure for observation.
6 is a thermogravimetric analysis graph of the complex of Example 1. Fig.
7 is a thermogravimetric analysis graph of the complex of Example 2. Fig.
8 is a thermogravimetric analysis graph of the complex of Example 3. Fig.
9 is a thermogravimetric analysis graph of the complex of Example 4. Fig.
10 is a thermogravimetric analysis graph of the complex of Example 5. Fig.
11 shows the fluorescence spectra at room temperature of the complexes of Examples 1 to 5 in the solid state and the flexible alpha, omega-alkane-dicarboxylic acid and bpa ligands used.
12 is a carbon dioxide adsorption isotherm graph of a complex compound of Example 4, (b) of Example 5 at (a) 196K, 273K and 298K temperatures.

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

The present invention relates to a complex of a compound selected from the group consisting of formulas (1) to (5) consisting of zinc and flexible alpha, omega-alkane-dicarboxylic acid and 1,2-bis (4-pyridyl)

[Chemical Formula 1]

[(Zn (H ₂ O) (μ-succinate) (μ-bpa)] 3 (H ₂ O)}]

(2)

[(Zn (H ₂ O) (μ-fumarate) (μ-bpa)] (H ₂ O)}]

(3)

[{Zn (H ₂ O) (μ-glutarate) (μ-bpa)}]

[Chemical Formula 4]

[{Zn (μ-adipate) (μ-bpa)] (H ₂ O)}]

[Chemical Formula 5]

[{Zn (μ-muconate) ₂ (μ-bpa) ₂ ] .4 (H ₂ O)}]

bpa is 1,2-bis (4-pyridyl) ethane.

The two-dimensional structure of [{Zn (H ₂ O) (μ-dicarboxylate)} _x (μ-bpa) _y. (H ₂ O) _z ] is a structure in which a dicarboxylic acid and a ligand are alternately combined to form a single plate. The two-dimensional plates are piled up to form a two-dimensional structure. Further, the three-dimensional structure of [{Zn (H ₂ O) (μ-dicarboxylate)} _x (μ-bpa) _y · (H ₂ O) _z ] is such that the plates of the two-dimensional structure are connected to each other by another ligand Structure. In the above Chemical Formulas 1 to 5 X-ray structure analysis, the two-dimensional structure of the formula (3) _{[{Zn (H 2 O)} (μ-dicarboxylate)} x (μ-bpa) y · (H 2 O) z] 1, 2, 4 and 5 have a three-dimensional structure of [{Zn (H ₂ O) (μ-dicarboxylate)} _x (μ-bpa) _y. (H ₂ O) _z ].

The asymmetric unit structure of Formula 1 includes one zinc ion, succinic acid, and bpa ligand, respectively, and three water molecules. The zinc ions are bridged with succinic acid and bpa ligand to form a three-dimensional structure (Fig. 1 (a)). These four three-dimensional structures penetrate each other (Fig. 1 (b) Is filled with water molecules. The three-dimensional structure from which the solvent has been removed has an empty space of 19.5%. The geometry of the zinc ion is a twisted tetrahedral structure due to two oxygen atoms of succinic acid and two nitrogen atoms of bpa ligand. The nitrogen-zinc-nitrogen bonding angle is 102.21 °, and the oxygen-zinc-oxygen bonding angle is 105.04 °.

The asymmetric unit structure of Formula 2 contains one zinc ion, one fumaric acid, one bpa ligand, and one water molecule. The zinc ion forms a three-dimensional structure by bridging fumaric acid and bpa ligand (Fig. 2 (a)). These five three-dimensional structures penetrate each other (Fig. 2 (b) Is filled with water molecules. The three-dimensional structure from which the solvent has been removed has an empty space of 7.2%. The geometry of the zinc ion is a twisted tetrahedral structure due to two oxygen atoms of fumaric acid and two nitrogen atoms of bpa ligand. The nitrogen-zinc-nitrogen bonding angle is 103.5 °, and the oxygen-zinc-oxygen bonding angle is 102.9 °.

The asymmetric unit structure of Formula 4 contains about half of zinc ion, about half of adipic acid, about half of bpa ligand and about half of water molecule. The zinc ion forms a three-dimensional structure by bridge bonding with adipic acid and bpa ligand (Fig. 4 (a)). These four three-dimensional structures penetrate each other (Fig. 4 (b) The space is filled with water molecules. The three-dimensional structure from which the solvent has been removed has an empty space of 22.1%. The geometry of the zinc ion is a distorted tetrahedral structure of two oxygen atoms of adipic acid and two nitrogen atoms of bpa ligand. The nitrogen-zinc-nitrogen bonding angle is 98.86 °, and the oxygen-zinc-oxygen bonding angle is 130.3 °.

The asymmetric unit structure of Formula 5 comprises two zinc ions, two muconic acids, two bpa ligands and four water molecules. 5 (a)). These five three-dimensional structures penetrate each other (FIG. 5 (b)) to form a void space, and the three- The space is filled with four water molecules. The three-dimensional structure from which the solvent has been removed has an empty space of 13.6%. The geometry of the zinc ion is a twisted tetrahedral structure due to two oxygen atoms of the muconic acid and two nitrogen atoms of the bpa ligand. The nitrogen-zinc-nitrogen bonding angles are 96.26 ° and 96.41 °, and the oxygen-zinc-oxygen bonding angles are 104.3 ° and 106.1 °.

On the other hand, Formula 3 has a two-dimensional structure. The asymmetric unit structure of Formula 3 includes two zinc ions, one glutaric acid, one bpa ligand, and two water molecules. Glutaric acid and bpa ligands bridge with zinc ions to form a two-dimensional layer structure (Fig. 3 (a)), and these two-dimensional layers penetrate each other (Fig. 3 (b)). The bonding angle of the oxygen atom of the glutaric acid to the oxygen atom of the zinc-glutaric acid is 92.97 to 122.71 and the bonding angle of the oxygen atom of the glutaric acid to the oxygen atom of the zinc-water molecule is 83.19 to 123.8 .

The bonding lengths and bonding angles of the complexes of the above Formulas 1 to 5 are shown in Table 1 below.

One 2 3 4 5 Zn-O (A) Zn-O _succ
1.9585 (15) -1.9882 (15) Zn-O _fuma
2002 (6),
2.036 (6) Zn-O _glut
1.954 (4) -2.012 (4)
(asymm.
2.418 (4), 2.469 (4))

Zn-O _water
1.973 (4)
Zn-O _adipine
1.905 (3) Zn-O _muco
1.918 (4) -1.967 (4) Zn-N (A) 2.0369 (17) -2.0653 (17) 2.017 (7),
2.060 (7) 2.048 (4), 2.056 (4)
2.060 (3) 2.037 (4) -2.056 (5) N-Zn-N (DEG) 102.21 (7) 103.5 (3) - 98.86 (16)
96.26 (17), 96.41 (18) O-Zn-O (DEG) 105.04 (7) O _glut- Zn-O _glut
83.19 (14) -123.8 (2)

O _glut- Zn-O _water
92.97 (18) -122.71 (1) - 130.3 (3) 104.3 (2), 106.1 (2)

As a result of TGA analysis, it was confirmed that Formulas 1 to 5 were thermally stable complex compounds.

The at least one complex compound selected from the group consisting of the compounds represented by formulas (1) to (5) of the present invention has a fluorescent dye property, and the complexes of the formulas (1), (3) and (4) preferably exhibit fluorescence properties. When the fluorescence intensities of the complex and flexible alpha, omega-alkane-dicarboxylic acid and bpa ligands were compared, the fluorescence of the complex was blue-shifted. In addition, the fluorescence intensity of the formula (3) was the largest, and the possibility of the mixed inorganic-organic photoactive material of the formula (3) was observed. Accordingly, the complex compound of the present invention can be used as a material for realizing the color of the display device. That is, the present invention can provide a display device including the fluorescent dye.

The present invention also relates to a carbon dioxide adsorbent comprising at least one complex selected from the group consisting of the above formulas (1) to (5), wherein Formulas (4) and (5) are preferably carbon dioxide adsorbents.

The carbon dioxide adsorbent can selectively adsorb carbon dioxide in the gas mixture and shows a higher adsorption rate as the temperature is lowered.

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>

[{Zn ( H ₂ O ) (μ- succinate ) (μ- bpa )] · 3 ( H ₂ O )}] And its crystal structure analysis

11.8 mg (0.1 mmol) of succinic acid and 30.4 mg (0.1 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O and 12.7 μL (0.1 mmol) of NH ₄ OH were dissolved in 4 mL of water, -Bipyridyl) ethane (37.2 mg, 0.2 mmol) was dissolved in 4 mL of acetonitrile solution. 30.4 mg of the compound of Formula 1 was obtained, and the crystal structure of Formula 1 was analyzed by X-ray analysis.

IR measurement results are as follows.

v (cm ^-1 ) = 3374 (brs), 1620 (m), 1580 (s), 1433 (w), 1402 (m), 1267 (w), 1072 ), 686 (s).

The results of elemental analysis of Formula 1 (C ₁₆ H ₂₂ N ₂ O ₇ Zn, molecular weight 419.73) were as follows.

Theoretical values: C, 45.78; H, 5.29; N, 6.68%

Found: C, 45.43; H, 5.63; N, 6.61%.

As a result of the elemental analysis, it can be considered that the complex of formula (1) is prepared.

< Example  2>

[{Zn ( H ₂ O ) (μ- fumarate ) (μ- bpa )] · ( H ₂ O )}] And its crystal structure analysis

8.1 mg (0.07 mmol) of fumaric acid and 21.2 mg (0.07 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O were dissolved in 4 mL of water and then 37.2 mg (0.2 mmol) was dissolved in 4 mL of acetonitrile solution. 12.1 mg of formula (2) was obtained, and the crystal structure of formula (2) was analyzed by X-ray analysis.

IR measurement results are as follows.

v (cm ^-1 ) = 1614 (w), 1579 (m), 1431 (w), 1368 (s), 1209 (w), 989 (w), 835 (m), 800 (m), 695 ).

The results of elemental analysis of Formula 2 (C ₁₆ H ₁₆ N ₂ O ₅ Zn, molecular weight 381.68) were as follows.

Theoretical values: C, 80.35; H, 4.23; N, 7.34%,

Experimental value: C, 50.48; H, 4.11; N, 7.62%.

As a result of the above elemental analysis, it can be considered that the complex of formula (2) is prepared.

< Example  3>

[{Zn ( H ₂ O ) (μ- glutarate ) (μ- bpa )}] And its structural analysis

13.3 mg (0.1 mmol) of glutaric acid and 30.4 mg (0.1 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O were dissolved in 4 mL of water and then 37.2 mg of 1,2-bis (4-pyridyl) 0.2 mmol) was slowly taken up in 4 mL of acetonitrile solution. 20.6 mg of Formula 3 was obtained and the crystal structure of Formula 3 was analyzed by X-ray analysis.

IR measurement results are as follows.

v (cm ^-1 ) = 1618 (w), 1580 (s), 1431 (w), 1407 (m), 1268 (w), 1231 (w), 1072 ), 686 (w).

The results of the elemental analysis of Formula 3 (C ₂₂ H ₂₈ N ₂ O ₁₀ Zn ₂ , molecular weight 611.20) were as follows.

Theoretical values: C, 43.23; H, 4.63; N, 4.63%

Found: C, 42.85; H, 4.87; N, 4.65%.

As a result of the above elemental analysis, it can be considered that the complex of formula (3) was prepared.

< Example  4>

[{Zn ([mu] adipate ) (μ- bpa )] · ( H ₂ O )}] And its structural analysis

14.6 mg (0.1 mmol) of adipic acid and 30.4 mg (0.1 mmol) of Zn (NO ₃ ) ₂ .6H ₂ O were dissolved in 4 mL of water and then 37.2 mg of 1,2-bis (4-pyridyl) 0.2 mmol) was slowly taken up in 4 mL of acetonitrile solution. 35.3 mg of the compound of Formula 4 was obtained, and the crystal structure of Formula 4 was analyzed by X-ray analysis.

IR measurement results are as follows.

v (cm ^-1 ) = 1584 (s), 1401 (m), 1269 (w), 1072 (w), 1028 (w), 834 (m), 687 (w), 644 (w).

Further, the elemental analysis results of the chemical formula 4 (C ₁₈ H ₂₀ N ₂ O ₄ Zn, molecular weight 411.75) were as follows.

Theoretical values: C, 52.50; H, 4.91; N, 6.81%

Found: C, 52.84; H, 5.32; N, 6.47%.

As a result of the above elemental analysis, it can be considered that the complex of formula (4) was prepared.

< Example  5>

[{ Zn (μ- muconate ) ₂ (μ- bpa ) ₂ ]·4( H ₂ O )}] And its structural analysis

10 mg (0.1 mmol) of muconic acid, 25.3 μL (0.2 mmol) of NH ₄ OH, 13.9 mg (0.1 mmol) of ZnCl ₂ and 37.2 mg (0.2 mmol) of 1,2- Of water. 5 mL of dimethylformamide was added to the solution to prepare a mixed solution, and the mixed solution was placed in a 20 cm ³ container. The inlet of the vessel was closed and heated to 85 ° C for 84 hours and then cooled to 25 ° C at a rate of 10 ° C / h. 23.6 mg of the compound of Formula 5 was obtained, and the crystal structure of Formula 5 was analyzed by X-ray analysis.

IR measurement results are as follows.

v (cm ^-1 ) = 3399 (br s), 1620 (s), 1559 (s), 1380 (s), 1293 (m), 1192 (w), 1005 (s), 866 ), 704 (w).

The results of elemental analysis of Formula 5 (C ₃₆ H ₄₀ N ₄ O ₁₂ Zn ₂ , molecular weight 851.46) were as follows.

Theoretical values: C, 50.78; H, 4.74; N, 6.58%

Experimental value: C, 50.66; H, 4.71; N, 6.45%.

As a result of the above elemental analysis, it can be considered that the complex of formula (5) is prepared.

Experimental Example  One. Example  Of the complex of 1 to 5 Thermal weight  analysis

The thermal stability of the complexes of Examples 1 to 5 was measured.

The TGA curve of the complex of Example 1 showed a loss of three water molecules of 10.75% (theoretical value: 12.88%) and a loss of three bpa molecules (theoretical value: 43.89%) of 43.75% ) And a loss of 20.63% of one succinic acid (theoretical value: 20.23) was observed at 411-800 ° C.

The TGA curve of the complex of Example 2 shows the loss of one water molecule (theoretical value: 4.72%) at 4.63% in the temperature range of 25-333 DEG C and one loss of bpa ligand at 333-389 DEG C for 47.75% 48.27%) and the loss of one malonic acid (theoretical value 21.5) was observed at 19.75% at 389-800 ℃.

The TGA curve of the complex of Example 3 showed a loss of one acetonitrile and water molecule (theoretical value: 5.90%) and a half of 30.13% at 130-360 ° C, respectively, in the temperature range of 73-130 ° C. and 5.88% The loss of 2-bis (4-pyridyl) ethane ligand (theoretical value of 30.14%) and the loss of two glutaric acids at 360-800 ° C (theoretical value: 37.33%) were observed.

The TGA curve of the complex of Example 4 showed a loss of 4.38% one water molecule (theoretical value: 4.38%) in the temperature range of 30-92 DEG C, one 1,2-bis (4- (Theoretical value: 44.74%) and a loss of adipic acid (theoretical value: 27.23%) at a multiplication of 27.13% at 309-800 DEG C was observed.

The TGA curve of the complex of Example 5 shows the loss of 6.39% of solvent molecules (six water molecules) (theoretical value: 6.35%) in the temperature range of 32-106 ° C, two water molecules of 69.17% at 106-800 ° C, Bis (4-pyridyl) ethane ligand, and loss of four muconic acids (theoretical value: 68.66%) were observed.

It can be seen from the above TGA measurement results that the complexes of Examples 1 to 5 are all thermally stable.

Experimental Example  2. Example  Fluorescence analysis of complexes of 1, 3 and 4

The fluorescence of the complexes of Examples 1, 3 and 4 and the flexible alpha, omega-alkane-dicarboxylic acid and 1,2-bis (4-pyridyl) ethone ligands was measured at room temperature in a solid state.

The emission of the complexes of Examples 1, 3 and 4 was carried out under the same experimental conditions and the results are shown in Table 2 below.

Complex The light emitting range (?) λ _ex Ligand The light emitting range (?) λ _ex Example 1 351-365 nm 322 nm Suche mountain 447-463 nm 322 nm Example 3 328 nm 328 nm Glutaric acid 447-463 nm 299 nm Example 4 370 nm 300 nm Adipic acid 447-463 nm 300 nm bpa ligand 447-463 nm 287 nm

The complexes of Examples 1, 3 and 4 exhibited fluorescence properties, and the emission band was shifted relative to the respective ligands to blue. This can be regarded as the emission peak of the above Examples 1, 3 and 4 by metal-to-ligand charge transfer (MLCT).

In addition, the complex of Example 3 exhibited stronger luminescence than that of the complexes of Examples 1 and 4 because the intensity of the complex of Example 3 was increased and energy loss due to non-radiation damping was reduced.

Thus, the strong luminescence of the complex of Example 3 can be shown to be useful as a mixed inorganic-organic photoactive material.

Experimental Example  3. Example  Carbon dioxide adsorption experiments using complexes of 4 and 5

The carbon dioxide adsorption ratios of the complexes of Examples 4 and 5 were measured.

The complexes of Examples 4 and 5 did not show adsorption of nitrogen gas at 77 K, but carbon dioxide gas showed a significant adsorption rate. At 196K, 273K, 298K in Example 4 complex were 79.9 cm ³ /g(3.56 mmol / g of ^{a), 41.1 cm 3 / g (} 1.84mmol / g), 35.2cm 3 / g (1.57mmol / g) It showed a carbon dioxide absorption rate of the complex in example 5 were ^{81.5 cm 3 / g (3.60mmol /} g), 16.9 cm 3 / g (0.75mmol / g), 10.69 cm 3 / g (0.48mmol / g) of Carbon dioxide adsorption rate. Both complexes showed an S-shaped carbon dioxide adsorption isotherm at 196K, and the adsorption rate increased as the temperature was lowered. In addition, the complex of Example 4 exhibited an isothermal S-shaped curve at 273 K despite a small amount of carbon dioxide adsorption. The S-curve isotherm appears to be due to the structural change of the compound or the electrostatic interaction of carbon dioxide molecules.

Claims (7)

delete delete A fluorescent dye comprising at least one complex selected from the group consisting of formulas (1), (3) and (4).
[Chemical Formula 1]
[(Zn (H ₂ O) (μ-succinate) (μ-bpa)] 3 (H ₂ O)}]
(3)
[{Zn (H ₂ O) (μ-glutarate) (μ-bpa)}]
[Chemical Formula 4]
[{Zn (μ-adipate) (μ-bpa)] (H ₂ O)}]
bpa is 1,2-bis (4-pyridyl) ethane. delete A display device comprising the fluorescent dye of claim 3. delete delete

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