METAL-ORGANIC HYBRID STRUCTURES BUILT WITH MULTI-DIRECTIONAL POLYDENTATE LIGANDS

Abstract

A compound represented by Chemical Formula 1 according to the present invention can coordinate with metal ions to form a bidirectional or multidirectional metal-organic hybrid structure. Thus, the present invention can synthesize various ligands using amine-aldehyde condensation, and synthesize metal-organic materials using the same.

Claims

1. A metal-organic hybrid structure formed by the coordinate bonding of a compound represented by the following Chemical Formula 1 or a salt thereof with metal ions: ##STR00010## in the Chemical Formula 1, R's are each independently R.sub.1, NHCOR.sub.2, or NHR.sub.2, R.sub.1's are each independently OH, a C.sub.6-60 aryl, a C.sub.1-10 alkyl, or an amino acid residue, and R.sub.2's are a C.sub.1-10 alkyl, a C.sub.6-60 aryl, or a C.sub.4-60 heteroaryl containing one of N, O, and S.

2. The metal-organic hybrid structure according to claim 1, wherein wherein R.sub.1's are each independently OH, phenyl, naphthyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, or an amino acid residue selected from the group consisting of alanine, cysteine, aspartic acid, glutamic acid, phenylalanine, histidine, isoleucine, lysine, leucine, methionine, asparagine, pyrrolysine, glutamine, arginine, serine, threonine, selenocysteine, valine, tryptophan, and tyrosine.

3. The metal-organic hybrid structure according to claim 1, wherein R.sub.2 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, hexyl, octyl, phenyl, naphthyl, or pyridinyl.

4. The metal-organic hybrid structure according to claim 1, wherein the compound represented by Chemical Formula 1 is a compound represented by one of the following Chemical Formulas 1-1 to 1-5: ##STR00011## ##STR00012##

5. The metal-organic hybrid structure according to claim 1, wherein the metal of the metal ion is Period 1 transition metal, Period 2 transition metal, Period 3 transition metal, or lanthanide metal.

6. The metal-organic hybrid structure according to claim 1, wherein the metal of the metal ion is Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, Ir, Pt, Au, Tb, Eu, or Yb.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0040] FIG. 1 shows the network structure formed by the coordination bond of the compound according to one embodiment of the present invention with metal ions.

[0041] FIG. 2 shows that the metal-organic hybrid structure of the present invention is prepared in the form of gel.

[0042] FIG. 3 shows the result of measuring fluorescence of the metal-organic hybrid structure of the present invention (terbium(III) metallogel) (solid fluorescence, absorption wavelength=450 nm, maximum emission wavelength=629 nm, baseline corrected).

[0043] FIG. 4 shows the result of observing the surface of the metal-organic hybrid structure of the present invention (cobalt(II) metallogel) with SEM.

[0044] FIG. 5 shows the result of observing the surface of the metal-organic hybrid structure of the present invention (nickel(II) metallogel) with SEM.

[0045] FIG. 6 shows the result of preparing the metal-organic hybrid structure of the present invention as a xerogel.

[0046] FIGS. 7 to 14 show the results of preparing the metal-organic hybrid structure of the present invention as a xerogel, and observing the surfaces with SEM.

[0047] FIGS. 15 to 23 show the results of preparing the metal-organic hybrid structure of the present invention as a xerogel, and observing the content of each element and the distribution in the sample with EDS (energy dispersive X-ray spectrometry).

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0048] Hereinafter, preferable examples are presented for better understanding of the present invention. However, these examples are presented only as illustrations of the present invention, and the scope of the present invention is not limited thereby.

Example 1

[0049] ##STR00005##

[0050] (Step 1)

[0051] HMTA (hexamethylenetetramine, 7.530 g, 53.70 mmol) was added into a dried round-bottom flask. The flask was purged with argon, and TFA (trifluoroacetic acid, 50 mL) was added. After completely dissolving HMTA, biphenyl-4,4-diol (1.000 g, 5.370 mmol) was rapidly added. After confirming that the mixture turned to an orange color, the mixture was heated at 120 C. for 7 days. The product was dark red, and it was poured into 4 N HCl (100 mL) to isolate the yellow precipitate. The precipitate was recrystallized with hot DMSO to obtain 2.460 g of yellow microcrystals (yield: 65.1%).

[0052] (Step 2)

[0053] The compound (0.296 g, 1.000 mmol) prepared in Step 1 and NH.sub.2OHHCl (0.420 g, 6.0 mmol) were added into a reactor. After adding water (7 mL), the mixture was heated to 80 C. Methanol was added dropwise until the mixture became transparent. After tightly sealing the reactor, the mixture was heated to 100 C. for 1 hour. After cooling to room temperature, water was added to induce precipitation. The solid material was isolated by filtration, and washed with water to obtain a light yellow product (powder, 0.360 g).

[0054] .sup.1H NMR (300 MHz, DMSO-d) 11.60 (s, 4H), 10.88 (s, 2H), 8.45 (s, 4H), 7.83 (s, 4H)

Example 2

[0055] ##STR00006##

[0056] Potassium hydroxide (6.80 mmol, 0.38 g) and 10 mL of ethanol were added into a reactor and stirred. Glycine (6.80 mmol, 0.510 g) was added to the mixture with stirring, and the mixture was stirred until solid materials were completely dissolved. A mixture in which tetraformylbiphenol (1.70 mmol, 0.500 g) prepared in Step 1 of Example 1 was dispersed in 10 mL of ethanol was separately prepared, and then it was slowly added to the reactor with stirring. During the addition, the mixture turned red. After the addition was finished, the mixture was poured into 20 mL of water, and then non-dissolved solid materials were removed by filtration. After removing water under reduced pressure, the remaining material was dispersed in a solvent of dimethylformamide and filtered to obtain a product in the form of an orange powder (0.4654 g, 74.6%).

[0057] .sup.1H NMR (300 MHz, D2O) 3.31 (s, 8H), 7.91 (s, 4H)

Example 3

[0058] ##STR00007##

[0059] 13 mL of ethanol was added into a reactor containing tetraformylbiphenol (0.500 g, 1.678 mmol) prepared in Step 1 of Example 1. While stirring the mixture, phenyl hydrazine (0.726 g, 6.710 mmol) was added with a syringe. The reactor was sealed and heated at 100 C. for 8 hours. The reaction mixture was cooled to room temperature, and then poured into 100 mL of water. The resulting precipitate was isolated by filtration, and washed with acetone to obtain a product in the form of a yellow powder (0.7797 g, 70.6%).

[0060] LC-MS: calculated for C.sub.40H.sub.34N.sub.8O.sub.2 [M].sup.+ 658.28, found 659.4.

Example 4

[0061] ##STR00008##

[0062] Tetraformylbiphenol (0.500 g, 1.678 mmol) prepared in Step 1 of Example 1 and nicotinic hydrazide (0.920 g, 6.710 mmol) were added into a reactor, and 13 mL of ethanol was added thereto. The reactor was sealed and heated at 100 C. for 8 hours. The reaction mixture was cooled to room temperature, and then poured into 100 mL of water. The precipitate was isolated by filtration, and washed with acetone to obtain the product in the form of a yellow powder (0.8971 g, 69.1%).

[0063] MALDI-TOF: calculated for C.sub.40H.sub.30N.sub.12O.sub.6 [M].sup.+ 774.24, found 775.5.

Example 5

[0064] ##STR00009##

[0065] Tetraformylbiphenol (0.500 g, 1.678 mmol) prepared in Step 1 of Example 1 and n-octanohydrazide (1.062 g, 6.710 mmol) were added into a reactor, and 13 mL of ethanol was added thereto. The reactor was sealed and heated at 100 C. for 8 hours. The reaction mixture was cooled to room temperature, and then poured into 100 mL of water. The precipitate was isolated by filtration, and washed with acetone to obtain a product in the form of a yellow powder (0.8072 g, 56.0%).

[0066] LC-MS: calculated for C.sub.48H.sub.74N.sub.8O.sub.6 [M]+ 858.57, found 859.7.

Experimental Example 1: Preparation of Gel

1) Experimental Example 1-1

[0067] The compound prepared in Example 1 (50.0 mg, 0.140 mmol) was added into a vial, and DMF (1.0 mL) was added to dissolve it. After adding triethylamine (0.12 mL, 0.840 mmol) dropwise and confirming that the solution turned to an orange color, the material of the following Table 1 was rapidly added. After stirring the mixture for 5 seconds, it was heated to 100 C. to form a gel, during which time the gel was gradually formed.

TABLE-US-00001 TABLE 1 Experimental Mn(OAc).sub.24H.sub.2O (90.0 mg, 0.240 mmol) Example 1-1 dissolved in DMF (3.0 mL)

2) Experimental Example 1-2

[0068] The compound prepared in Example 1 (50.0 mg, 0.140 mmol) was added into a vial, and DMF (1.0 mL) was added to dissolve it. After it was completely dissolved, the material of the following Table 2 was added. Thereafter, triethylamine (0.12 mL, 0.840 mmol) was rapidly added dropwise, and immediately after the addition, a black gel was formed. After stirring the mixture for 5 seconds, it was heated to 100 C. for homogenization of a gel and an increase in the strength thereof. After about 1 hour, the gelation process was completed.

TABLE-US-00002 TABLE 2 Experimental FeCl.sub.2 (90.0 mg, 0.240 mmol) Example 1-2 dissolved in DMF (3.0 mL)

3) Experimental Examples 1-3 to 1-6

[0069] The compound prepared in Example 1 (50.0 mg, 0.140 mmol) was added into a vial, and DMF (1.0 mL) was put therein to dissolve it. After adding triethylamine (0.12 mL, 0.840 mmol) dropwise and confirming that the solution turned to an orange color, the materials of the following Table 3 were rapidly added. Immediately after the addition, a gel began to form. After stirring the mixture for 5 seconds, it was heated to 100 C. for the homogenization of the gel and an increase in the strength thereof. After about 1 hour, the gelation process was completed.

TABLE-US-00003 TABLE 3 Experimental CO(OAc).sub.24H.sub.2O (90.0 mg, 0.280 mmol) Example 1-3 dissolved in DMF (3.0 mL) Experimental Ni(OAc).sub.24H.sub.2O (140.0 mg, 0.420 mmol) Example 1-4 dissolved in DMF (3.0 mL) Experimental Cu(OAc).sub.2H.sub.2O (140.0 mg, 0.420 mmol) Example 1-5 dissolved in DMF (3.0 mL) Experimental Zn(OAc).sub.22H.sub.2O (140.0 mg, 0.420 mmol) Example 1-6 dissolved in DMF (3.0 mL)

[0070] Each gel prepared in Experimental Examples 1-1, 1-3, 1-4, and 1-6 are shown in FIG. 2. As shown in FIG. 2, each metal-organic hybrid structure was prepared in the form of a gel.

4) Experimental Examples 1-7 to 1-10

[0071] The compound prepared in Example 1 (50.0 mg, 0.140 mmol) was added into a vial, and DMF (1.0 mL) was added to dissolve it. After adding a solution of sodium methoxide (22.5 mL, 0.420 mmol) in 1.0 mL of ethanol dropwise and confirming that the solution turned to an orange color, the materials of the following Table 4 were rapidly added. Immediately after the addition, a gel began to form. After stirring the mixture for 5 seconds, it was heated to 100 C. for the homogenization of the gel and an increase in the strength thereof. After about 1 hour, the gelation process was completed.

TABLE-US-00004 TABLE 4 Experimental Pd(OAc).sub.2 (95.0 mg, 0.420 mmol) Example 1-7 dissolved in DMF (3.0 mL) Experimental Ru(acac).sub.3 (113.0 mg, 0.280 mmol) Example 1-8 dissolved in DMF (3.0 mL) Experimental Tb(NO.sub.3).sub.35H.sub.2O (122.0 mg, 0.280 mmol) Example 1-9 dissolved in DMF (3.0 mL) Experimental Eu(NO.sub.3).sub.35H.sub.2O (119.0 mg, 0.280 mmol) Example 1-10 dissolved in DMF (3.0 mL)

Experimental Example 2: Measurement of Fluorescence of Gel

[0072] The gel prepared in Experimental Example 1-9 was applied on a slide glass, and then dried in a vacuum oven at 80 C. for 2 hours. The fluorescence spectrum of the dried gel was measured, an excitation wavelength was 450 nm, and a maximum emission wavelength was 629 nm as shown in FIG. 3.

Experimental Example 3: Observation of the SEM Image of the Gel

1) Experimental Example 3-1

[0073] A cobalt gel prepared in Experimental Example 1-3 was dried under vacuum for 12 hours, and a SEM image was obtained using the product. Specifically, the dried gel was dispersed in a stub, to which a carbon double-sided tape was attached, and coated with platinum, and it was observed under a 15 kV voltage condition. The result is shown in FIG. 4.

2) Experimental Example 3-2

[0074] A nickel gel prepared in Experimental Example 1-4 was dried under vacuum for 12 hours, and a SEM image was obtained using the product. Specifically, the dried gel was dispersed in a stub, to which a carbon double-sided tape was attached, and coated with platinum, and it was observed under a 5-15 kV voltage condition. The result is shown in FIG. 5.

Experimental Example 4: Preparation of Xerogel

[0075] The gels prepared in Experimental Examples 1-2 to 1-10 were treated with supercritical carbon dioxide to remove the solvent, thus preparing xerogels. Specifically, the above prepared gel was loaded into a cylinder made of stainless steel, and then it was installed inside a supercritical carbon dioxide apparatus. At 40 C., 200 atm of supercritical carbon dioxide was flowed at a rate of 0.1 mL/minute to remove the solvent, thus obtaining a product in the form of a powder. The results of observing a part of them with the unaided eyes are shown in FIG. 6.

Experimental Example 5: Analysis of Xerogel

[0076] Using the xerogel prepared in Experimental Example 4, a SEM image was obtained. Specifically, the xerogel was dispersed in a stub, to which a carbon double-sided tape was attached, coated with platinum, and it was observed under a 5-15 kV voltage condition, and the results are shown in FIGS. 7-15. Simultaneously, the element distribution of the xerogel surface was measured by EDS (energy dispersive X-ray spectroscopy), and the results are shown in FIGS. 16-23. The contents of each drawing are as described in the following Table. 5.

TABLE-US-00005 TABLE 5 SEM EDS Element component SEM image distribution mapping Xerogel (Fe xerogel) of FIG. 7 FIG. 16a FIG. 16b Experimental Example 1-2 Xerogel (Co xerogel) of FIG. 8 FIG. 17a FIG. 17b Experimental Example 1-3 Xerogel (Ni xerogel) of FIG. 9 Experimental Example 1-4 Xerogel (Cu xerogel) of FIG. 10 FIG. 18a FIG. 18b Experimental Example 1-5 Xerogel (Zn xerogel) of FIG. 11 FIG. 19a FIG. 19b Experimental Example 1-6 Xerogel (Pd xerogel) of FIG. 12 FIG. 20a FIG. 20b Experimental Example 1-7 Xerogel (Ru xerogel)of FIG. 13 FIG. 21a FIG. 21b Experimental Example 1-8 Xerogel (Tb xerogel) of FIG. 14 FIG. 22a FIG. 22b Experimental Example 1-9 Xerogel (Eu xerogel) of FIG. 15 FIG. 23a FIG. 23b Experimental Example 1-10