KR101176875B1 - Mixed-ligand metal-organic frameworks with large pores - Google Patents

Abstract

The present invention relates to a non-invasive 3D skeleton having a large pore of an effective size, and relates to a mixed-ligand metal organic framework for gas storage, gas separation, and sensor, and specifically, a non-invasive 3D represented by [Formula 1] It relates to a mixed-ligand metal-organic framework or solvate thereof having a framework and having large pores. The mixed-ligand metal-organic framework of the present invention forms a non-invasive 3D framework with large free spaces and large pores of effective size, so that it can be adsorbed and separated as a gas reservoir, ion exchange, catalyst, sensor, crystallography. It is a gas storage body that can be usefully used in such fields.

Metal-organic framework, gas storage and separation

Description

Mixed-ligand metal-organic frameworks with large pores

The present invention relates to a non-invasive 3D skeleton having a large pore size of effective size, and relates to a mixed-ligand metal organic framework for gas storage and a sensor, and specifically, to a non-invasive 3D skeleton represented by [Formula 1]. A mixed-ligand metal-organic framework having pores or a solvate thereof.

Metal-organic frameworks (MOFs) are a type of coordination polymer compound composed of metal salts and organic ligands, which can cover a variety of coordination structures ranging from linear primary structures, platelike secondary structures, and complex three-dimensional structures. Form.

When such metal-organic frameworks have permanent porosity, they have been widely studied because they have potential applications in various fields such as molecular adsorption and separation processes, optoelectronics and the like.

The purpose of building MOFs is to obtain materials with characteristic and multifunctional properties. In particular, gas storage (Lee, EY; Jang, SY; Suh, MP J. Am. Chem. Soc . 2005, 127, 6374-6381) and separation (Suh, MP; Cheon, YE; Lee, EY Chem. Eur) J. 2007, 13, 4208-4215), selective adsorption and separation of organic molecules (Lee, JY; Olson, DH; Pan, L .; Ernge, TJ; Li, J. Adv.Funct . Mater . 2007, 17 1255-1262), ion exchange (Min, KS; Suh, MP J. Am. Chem. Soc . 2000, 122, 6834-6840) and catalysts (Wu, CD; Hu, A .; Zhang, L .; Lin , W. J. Am. Chem. Soc. 2005, 127, 8940-8941) and sensor technology (Lee, EY; Jang, SY; Suh, MP J. Am. Chem. Soc. 2005, 127, 6374-6381. ; Bauer, CA; Timofeeva, TV; Settersten, TB; Patterson, BD; Liu, VH; Simmons, BA; Allendorf, MD J. Am. Chem. Soc . 2007, 129, 7136-7144) MOFs that include free space for object molecules have attracted attention.

The design of MOFs as functional materials can be achieved by the selection of suitable metal and organic building blocks. In particular, secondary building units with specific structures are useful for obtaining reasonably designed MOFs because they significantly improve the predictability of the molecular structure. Among the many functions of porous MOFs, hydrogen storage has been at the center of attention because of the demand as an alternative fuel applicable to automobiles. The US Department of Energy aims to develop a material capable of storing 6.0 percent by weight or 45 gL ^-1 of hydrogen gas at ambient temperature by 2010. In addition, since carbon dioxide gas is the main source of greenhouse gas emissions, the selective adsorption of carbon dioxide from the gas mixture is very important. The highest hydrogen gas uptake data reported so far is 7.5 at 77 K and 70 bar in MOF-177 (AG Wong-Foy; AJ Matzger; OM Yaghi, J. Am. Chem. Soc . 2006, 128. 3494-3495). Weight percent. However, room temperature stored data is less than 1% (0.62 wt.%). The highest carbon dioxide gas uptake data reported so far is 298 K at MOF-177 and 147 wt% at 35 bar. Recently, flexible and dynamic MOFs that possess single crystals and that can change their structure in response to external stimuli have become important for the development of specific designs and sensors.

Accordingly, the present inventors have conducted extensive research to solve the above-mentioned problems. As a result, since the metal-organic framework according to the present invention has a permanent porosity, it can be usefully used as a reservoir of various gases and is transformed into a single crystal. It was confirmed that the present invention can be applied to the development of crystallography and sensors, and eventually the present invention was completed.

There is an increasing demand for a functional metal-organic framework capable of maintaining a gas storage body and a single crystal having excellent storage capacity and capable of changing its structure in response to external stimuli. The present invention has been made to solve the conventional problems and to provide a metal-organic framework for gas storage, gas separation or sensor having a large free space and effectively having a large pore size.

The present invention relates to a porous mixed-ligand metal-organic framework or a solvate thereof which is a non-invasive 3D framework represented by the following [Formula 1].

{[M ₂ (L1) ₂ (L2)] X (Sol1)? Y (Sol2)} _n

Wherein M is any one selected from the group consisting of Cu, Zn, Cd, Ni, Co, Mn, Ca and Mg; L1 is BPnDC, bis (4-carboxyphenyl) methane, N, N-bis (4-carboxyphenyl) amine, 1,1-bis (4-carboxyphenyl) ethylene and 4,4'-oxybis (benzoic acid Any one selected from the group consisting of L2 is pyrazine, 4,4'-bipyridine, 4-diazabicyclo [2,2,2] octane, trans-1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridine) Dill) ethane, 1,3-bis (4-pyridyl) propane, 3,6-bis (4-pyridyl) -1,2,4,5-tetrazine, 4,4`-azodipyridyl and Any one selected from the group consisting of 4,4′-dipyridylamine; Sol1 and Sol2 consist of methanol, ethanol, butanol, acetonitrile, methylene chloride, chloroform, toluene, benzene, acetone, n-hexane, dodecane, THF, ether, water, dioxane, pyridine, DEF, DMA, DEA and DMF Any one selected from the group; X and Y are each an integer up to 0-20, preferably an integer up to 0-15, more preferably an integer up to 0-10; n is an integer of 0 or more.

The mixed-ligand metal-organic framework of the present invention forms a non-invasive 3D framework with large free spaces and large pores of effective size, so that it can be adsorbed and separated as a gas reservoir, ion exchange, catalyst, sensor, crystallography. It is a gas storage body that can be usefully used in such fields.

The present invention relates to mixed-ligand metal organic frameworks for gas storage and sensors, as non-invasive 3D frameworks having large pores of effective size.

Hereinafter, the present invention will be described in detail.

Metal-organic frameworks often decay when the object molecules that occupy their space are removed, are easily destroyed under vacuum at high or even low temperatures due to heat instability, often dissolved in solvents and dissociated into building units On the other hand, the metal-organic frameworks according to the invention have this instability resolved and have a substantially permanent porosity. Therefore, in the present invention, the expression "permanent porous framework" and the like refers to a framework in which such instability is resolved to obtain a substantially permanent porosity, and has a permanent porosity under any extreme conditions or a condition such as heat. This does not mean absolute stability that is not destroyed at all. Whether the metal-organic framework is substantially permanently porous or otherwise easily decomposed due to temperature, pressure, or solvent conditions can be easily determined through simple experiments. As it is widely used in the field, it will be easily understood by those skilled in the art.

Metal-organic frameworks with large pores are often unstable. In order to solve this problem, independent structures are intertwined or interpenetrated. However, the problem of these twisted skeletons is that the pores cannot store or store pores even if they have pores for storing gas or organic molecules. However, the frameworks of the present invention can be used for gas storage and sensors by non-interpenetrating while having large pores greater than 1 nm (1: 18.2 mm 3, 2: 11.4 mm 3).

Therefore, in the present invention, the "non-invasive" 3D skeleton is significantly reduced so that it can be seen that there are substantially no problems with the conventional skeletons, that is, the problems of twisting or penetrating the independent structures are relatively large pores. Eggplant means a 3D framework, and this meaning is commonly used in the art to which the present invention belongs and can be said to be easily understood by those skilled in the art.

Typically, high pressure means a pressure around 120 bar, medium and low pressure means a pressure around 30 bar, 0.1 bar, respectively, and in the present invention, high pressure, medium pressure, low pressure, unless otherwise indicated in the corresponding parts It can be seen as a range.

One aspect of the present invention relates to a mixed-ligand metal-organic framework or solvate thereof, which is a non-invasive 3D framework represented by the following [Formula 1] and has large pores.

[Formula 1]

{[M ₂ (L1) ₂ (L2)] X (Sol1)? Y (Sol2)} _n

M is any one selected from the group consisting of Cu, Zn, Cd, Ni, Co, Mn, Ca and Mg; L1 is BPnDC, bis (4-carboxyphenyl) methane, N, N-bis (4-carboxyphenyl) amine, 1,1-bis (4-carboxyphenyl) ethylene and 4,4'-oxybis (benzoic acid) Any one selected from the group consisting of; L2 is pyrazine, 4,4'-bipyridine, 4-diazabicyclo [2,2,2] octane, trans-1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridine) Dill) ethane, 1,3-bis (4-pyridyl) propane, 3,6-bis (4-pyridyl) -1,2,4,5-tetrazine, 4,4`-azodipyridyl And 4,4′-dipyridylamine; Sol1 and Sol2 consist of methanol, ethanol, butanol, acetonitrile, methylene chloride, chloroform, toluene, benzene, acetone, n-hexane, dodecane, THF, ether, water, dioxane, pyridine, DEF, DMA, DEA and DMF Any one selected from the group; X and Y are each an integer up to 0-20, preferably an integer up to 0-15, more preferably an integer up to 0-10; n is an integer of 0 or more.

According to an embodiment of the present invention, the metal-organic skeleton of [Formula 1] has a Langmuir surface area of 2000-4500 m ² g ⁻¹ , preferably 2500-4450 m ² g ⁻¹ ; The BET surface area is 1500-3500 m ² g ⁻¹ , preferably 2000-3400 m ² g ⁻¹ ; The duvinin-radsukebeach pore volume is 0.3-3.0 cm ³ g ⁻¹ , preferably 0.4-2.8 cm ³ g ⁻¹ ; The total free space is 60-90%, preferably 65-85% and has an isoarrangement of 5-12 kJmol ^-1 , preferably 7-10 kJmol ^-1 ; The pore size is 8-30 mm 3, preferably 10-30 mm 3.

In the present invention, there is a case in which the physical properties such as surface area, void volume, total free space, arrangement interval, and pore size are described in a certain range as an expression of a preferred embodiment, and such physical properties are limited to the scope of the present invention. Only have the ability to form non-invasive 3D frameworks with larger free spaces and large pores of effective size, such that adsorption and separation, ion exchange, catalysts, It can be usefully used in the fields of sensors, crystallization design, and the like.

Although the physical properties in the above ranges could not be achieved at all in the metal-organic framework of the same structure in the past, the physical properties could be prepared by following the specific process described in the Examples of the present invention, but the present invention is It cannot be interpreted as being limited by the manufacturing method, and it can be said that it can be said that it contains all the compounds which have the said structure and satisfy | fill the said physical property.

In addition, the metal organic framework of [Formula 1] is hydrogen adsorption capacity of 4% by weight or more at 77 K and 70 bar, it is preferable that the carbon dioxide adsorption capacity is 100% by weight or more at 195 K and 1 atm.

In addition, the metal-organic framework according to the present invention may significantly vary in structure and physical properties according to the preparation method thereof, and thus, the solvate of [Formula 1] is heated under a vacuum of 80-120 ° C. for 1-4 hours. It is very preferable to manufacture the following [Formula 2] by desolvation.

[M ₂ (L1) ₂ (L2)] _n

In the present invention, BPnDC is benzophenone 4,4'-dicarboxylic acid, bpy is 4,4'-bipyridine, and dabco is 4-diazabicyclo. [2,2,2] octane (4-diazabicyclo [2,2,2] octane), THF is tetrahydrofuran, DEF is diethylformamide, DMA is dimethyl acetamide ), DEA means diethanol amine, DMF means dimethylformamide.

According to one embodiment of the present invention, the metal-organic skeleton of [Formula 1] relates to a metal-organic skeleton represented by the following [Formula 3].

[Cu ₂ (BPnDC) ₂ (bpy)] _n

The metal-organic framework of [Formula 3] has a Langmuir surface area of 2500-3500 m ² g ⁻¹ , a BET surface area of 2000-3000 m ² g ⁻¹ , and a Dubinin-Radschkevic pore volume of 0.5- 2.0 cm ³ g ⁻¹ , total free space is 75-90%, has an equi ^- array of 6-10 kJmol ⁻¹ and a pore size of 10-25 mm ³ .

In addition, the metal-organic framework of [Formula 3] is hydrogen adsorption capacity of 4% by weight or more at 77 K and 70 bar, carbon dioxide adsorption capacity is more than 110% by weight at 195 K and 1 atm.

The metal-organic skeleton of [Formula 3] is preferably prepared by heating the solvate of [Formula 4] under a vacuum of 80-120 ° C. for 1-4 hours to desolvate it.

{[Cu ₂ (BPnDC) ₂ (bpy)]? 8DMF? 6H ₂ O} _n

Another embodiment of the present invention relates to a metal-organic skeleton, wherein the metal-organic skeleton of [Formula 1] is represented by the following [Formula 5].

{[Zn ₂ (BPnDC) ₂ (dabco)]? 6 (n-hexane)? 3H ₂ O} _n

The metal-organic skeleton of [Formula 5] is 70-85% of the total free space, it is preferable that the pore size is 5-15 Å.

The metal-organic skeleton of [Formula 5] is preferably prepared by exchanging DMF of [Formula 6] with n-hexane.

{[Zn ₂ (BPnDC) ₂ (dabco)]? 13DMF? 3H ₂ O} _n

[Formula 6] is the DMF object molecules are exchanged with n-hexane to form the formula [5]. In the structure of [Formula 5], the rectangular plane of the outer ring unit is bent in the structure of [Formula 6], which is due to the rotation rearrangement of the carboxyl group and the phenyl ring of BPnDC ^2- . When the n-hexane of [Formula 5] is released into the air, the structure of the skeleton is modified, and when all the object molecules are removed, it is changed similarly to [Zn ₂ (BPnDC) ₂ (dabco)] _n (2a). That is, as the object molecules are removed, the structure of the single crystal of the skeleton is changed, and the structure of the skeleton is changed.

Another embodiment of the present invention relates to a metal-organic skeleton, wherein the metal-organic skeleton of [Formula 1] is represented by the following [Formula 7], [Formula 8] and [Formula 9]. .

{[Ni ₂ (bis (4-carboxyphenyl) methane) ₂ (trans-1,2-bis (4-pyridyl) ethylene)]? X (BuOH)? YH ₂ O} n

The metal-organic skeleton of [Formula 7] is 60-75% of the total free space, and the pore size is preferably 4-10 mm 3.

{[Cd ₂ (N, N-bis (4-carboxyphenyl) amine) ₂ (1,2-bis (4-pyridyl) ethane)]? X (THF)? Y (EtOH)} n

The metal-organic skeleton of [Formula 8] has a total free space of 60-70% and a pore size of 3-11 Å.

{[Co ₂ (1,1-bis (4-carboxyphenyl) ethylene) ₂ (bpy)]? X (n-hexane)? Y (toluene)} n

The metal-organic skeleton of [Formula 9] is 63-72% of the total free space, the pore size is preferably 5-13 Å.

Another aspect of the present invention is a gas device using the gas storage body containing the metal-organic framework of the formula [1] includes a gas device, such as a gas reservoir, a gas separation device, a gas sensor device.

The gas is particularly preferably selected from nitrogen, carbon dioxide, methane, hydrogen and mixtures thereof. In particular, as confirmed in the following experimental example, the difference between the carbon dioxide and methane adsorption capacity of [Formula 3] can be usefully applied to the gas separation process.

[Example]

The following examples are intended to specifically describe the contents of the present invention, whereby the scope of the present invention is never limited and can be interpreted.

In particular, if a compound belonging to the present invention is not described in the following Preparation Examples, Examples, and Experimental Examples, based on the disclosure of the present invention, those skilled in the art to which the present invention pertains are based on common knowledge in the art. It can be said that it can be easily manufactured and obtained.

In the examples below, all chemicals and solvents used in the synthesis were used as reagent grade without further purification. Infrared spectroscopy was performed using a Perkin Elmer Spectrum One FT-IR spectrophotometer, and the UV / vis diffuse reflectance spectra were recorded with a Perkin Elmer Lambda 35 US / vis spectrophotometer. Basic analysis was performed with a Perkin Elmer EA 2400 analyzer. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed using TA Instruments' TGA Q50 and DSC Q10. Each under a nitrogen atmosphere at a scan rate of 5 ° C./min. Powder X-ray diffraction ('PXRD') results were obtained using a Bruker D5005 diffractometer with a scan rate of 5 ^o / min for Cu Ka (= 1.54050 kPa) at 40 kV and 40 mA, The step size was measured at 2θ to 0.02 ^o .

Example 1: {[Cu ₂ (BPnDC) ₂ (bpy)]? 8DMF? 6H ₂ Preparation of O} n (1)

H ₂ BPnDC (0.056 g, 2.1x10 ^-4 mol) and 4,4'-bpy (0.018 g, 1.2x10 ^-4 mol) were dissolved in DMF (6 mL) and Cu (NO ₃ ) ₂ -2.5H ₂ O (0.061 g, 3.3 × 10 ⁻⁴ mol) was dissolved in 3 mL of ethanol. The solutions were mixed with each other, tightly capped with a silicone stopper and aluminum, placed in a glass serum bottle and heated at 80 ° C. for 24 hours. Cooling to room temperature gave blue diamond crystals which were filtered off and quickly washed off with DMF.

Yield: 0.13 g, 82%

FT-IR (Nujol) for 1: ν = 3436 (OH), ν = 1667 (br, C = O (DMF), C = O (BPnDC)), ν = 1628 (C = O), ν = 1608 (OC = O (carboxylate)), ν = 1559 (C = C (aromatic)) cm ⁻¹ ; UV / Vis (Diffuse reflectance, λmax) = 272, 745 nm

Elemental analysis (calculated) (%) for Cu ₂ C ₆₄ H ₉₂ O ₂₄ N ₁₀ : C 50.82, H 6.13, N 9.26

Elemental Analysis (Actual): C, 51.04; H, 5. 60; N, 9.17

Example 2: [Cu ₂ (BPnDC) ₂ (bpy)] Preparation of n (1a)

1 was heated in a Schlenk tube at 100 ° C. for 2 hours under vacuum.

FT-IR (Nujol): ν = 1668, 1631 (C = O)), ν = 1606, 1561 (OC = O (carboxylate)), ν = 1559 (C = C (aromatic)) cm ^-1

UV / Vis (Diffuse reflectance, λmax) = 272, 735 nm

Elemental analysis for Cu ₂ C ₄₀ H ₂₄ O ₁₀ N ₂ (calculated): C, 58.61; H, 2.95; N, 3.42

Elemental Analysis (Actual): C, 57.48; H, 2.87; N, 3.20

Example 3: {[Zn ₂ (BPnDC) ₂ (dabco)]? 13DMF? 3H ₂ Preparation of O} n (2)

H ₂ BPnDC (0.053 g, 2.0x10 ^-4 mol) and dabco (0.015 g, 1.3x10 ^-4 mol) were dissolved in 3 mL of DMF, Zn (NO ₃ ) ₂ -H ₂ O (0.077 g, 2.6 x 10 ^-4 mol) was dissolved in 2 mL of DMF. The solutions were mixed with each other, tightly capped with a silicone stopper and aluminum, placed in a glass serum bottle and heated at 100 ° C. for 3 days. Cooling to room temperature formed colorless diamond crystals which were filtered and quickly washed off with DMF.

Yield: 0.12 g, 67%

FT-IR (Nujol) for 2: v = 3436 (OH), v = 2952, 2924, 2854 (CH (aliphatic)), v = 1665 (br, C = O (DMF), C = O (BPnDC) ), ν = 1604 (OC = O (carboxylate)), ν = 1541 (C = C (aromatic)) cm ^-1

Elemental Analysis (calculated) (%) for Zn ₂ C ₇₅ H ₁₂₅ O ₂₆ N ₁₅ : C, 50.50; H, 7.06; N, 11.78

Elemental Analysis (Actual): C, 50.71; H, 6.87; N, 11.78

Preparation Example 1 [Zn ₂ (BPnDC) ₂ Preparation of (dabco)] n (2a)

2 was heated in a Schlenk tube at 100 ° C. for 2 hours under vacuum.

FT-IR (Nujol): ν = 1638 (C = O), ν = 1600, 1549 (OC = O (carboxylate)) cm ^-1

Elemental Analysis (calculated) (%) for Zn ₂ C ₃₆ H ₂₈ O ₁₀ N ₂ : C, 55.48; H, 3.62; N, 3.59

Elemental Analysis (Actual): C, 54.13; H, 4.13; N, 3.54

Example 4: {[Zn ₂ (BPnDC) ₂ (dabco)]? 6 (n-hexane)? 3H ₂ Preparation of O} n (2b)

Crystal of 2 was placed in n-hexane for 24 hours, then the solvent was discarded and fed with fresh n-hexane. The crystals were left in the solvent for 2 days until all DMF object molecules were exchanged with n-hexane.

FT-IR (Nujol): ν = 1642 (C = O), ν = 1610, 1554 (OC = O (carboxylate)) cm ^-1

Elemental Analysis (calculated) (%) for Zn ₂ C ₇₂ H ₁₁₈ O ₁₃ N ₂ : C, 62.70; H, 8. 29; N, 2.22

Elemental Analysis (Actual): C, 62.49; H, 7.80; N, 2.19

Experimental Example 1 Crystal Structure Analysis of Solid 1, Solid 2, Solid 3, Solid 4, and Solid 5 by X-ray Diffraction

X of Example 1 (1), Example 3 (2), Example 4 (2b), Example 5 (3), Example 6 (4) and Example 7 (5) The -ray diffraction data were collected on an Enraf Nonius Kappa CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 kPa). Single crystals of 1, 2, 2b, 3, 4 and 5 were sealed together in an organic capillary together with the mother liquor. Preliminary bias metrics and unit cell parameters were obtained from peaks of the first 10 frames and purified using the full data set. Frames are described by Z. Otwinowsky, et al. The integrated and collected using DENZO described by Academic Press, 1996, 276, 307-326, and the scale and extensive purification of crystal parameters were performed by SCALEPACK. No adsorption collection was made. Sheldrick, G. M. Acta Crystallogr. Crystal structures were analyzed by the direct method described in 1990, A46, 467-473, and analyzed in detail by full-matrix least-squares using the SHELXL-97 computer program. The density of the disordered object molecules present at 1, 2, 2b, 3, 4 and 5 was lowered by selecting SQUEEZE of PLATON.

For 1, the two carbon atoms of 4,4'-bpy were rotatively disordered twice. The location control elements were given 0.5 for C9A, C9B, C10A and C10B. All positions without hydrogen atoms were purified with anisotropic substitution elements. Hydrogen atoms were geographically located using the riding model. The densities of disordered object molecules at 1, 2, 2b, 3, 4 and 5 were scattered using PLATON's SQUEEZE selection. CCDC-689692 (A), -689693 (B), -689694 (1), -689695 (2) and -689696 (2b) include additional crystallographic data in the present invention. These data were obtained from the Cambridge Crystallographic Data Center at www.ccdc.cam.ac.uk/data_request/cif.

1-1: {[Cu ₂ (BPnDC) ₂ (bpy)]? 8DMF? 6H ₂ X-ray Structure and Properties of O} n (1)

The cut off octahedral blue crystals of ₁ were prepared by heating a DMF / EtOH solution of Cu (NO ₃ ) ₂ -2.5H ₂ O, H ₂ B PnDC and 4,4′-bipyridine for 24 hours at 80 ° C. As shown in FIG. 1, the single crystal X-ray structure of 1 showed a non-invasive 3D coordination network. At 1, Cu ^II exhibited a tetragonal pyramidal coordination structure by coordinating with a nitrogen atom of 4,4'-bpy at the axis position and four oxygen atoms of four different BPnDC ^2- ligands at the equator position. The Cu-O _BPnDC2- bond distance is on average 1.974 (2) kPa, and the Cu-N _bpy bond distance is -2.161 (4) kPa. BPnDC ^2- is two bidentate ligands and coordinated with four other Cu ^II centers. Each carboxyl group of four BPnDC ^2- is connected to two Cu ^II centers to form the outer ring of SBU, Cu ^II -Cu ^II distance is 2.669 (1) Å, BPnDC ^2- is the 휜 linker (linker) and two phenyl The back angle between the rings was 67.69 (14) degrees.

The backside angle between adjacent rectangular planes formed by the carboxyl group carbon atoms of the outer ring SBU was 90.00 (0) °, which resulted in a 3D network. In general, 2D layers are formed from M2 units and dicarboxylate linkers of the outer ring lysate of the nucleus, and 3D initial volume MOFs could be constructed by connecting diamine pillars to the 2D layers. The present experiment also showed that the solvent thermal reaction of Cu (NO ₃ ) _{2 to} 2.5H ₂ O and H ₂ BPnDC in a DEF / EtOH mixture or DMA in the absence of diamines was observed in 2D network {[Cu ₂ (BPnDC) ₂ (DEF) ₂ ]? 2DEF} n (A) and {[Cu ₂ (BPnDC) ₂ (DMA) ₂ ]? 4DMA} n (B). The X-ray structures of A and B showed that the outer ring nucleus Cu2 units were connected by BPnDC ^2- to form a curved 2D 44-grid. Therefore, 2D sheets were expected to be further connected by 4,4'-bpy columns to construct 3D frameworks.

However, at 1 Cu ₂ outer ring SBUs were connected with BPnDC ²⁻ to form 3D frameworks themselves. Ligands linked in a straight line of paddle units had a significant effect on paddle position at 1. As shown in Fig. 1c, the eight quadrangular surfaces formed by the carboxyl group carbon atoms of the outer ring SBU form a rhombus, where the quadrangular surfaces are repeatedly placed at a dihedral angle of 90.00 (0) ° on the ac- and bc-planes. The set of quadrilaterals (S1 and S5), (S2, S4, S6 and S8) and (S3 and S7) respectively extended along the a-, b- and c-axis. Parallel squares such as (S2 and S4) and (S6 and S8) were connected to the 4,4'-bpy connector to create two channels with triangular and hexagonal gaps, which resulted in a Kagome net. It was. The effective ends of the lengths and the small triangular channels are approximately 10.7 and 5.6 ,, and the large hexagonal channel has a width of 21.6 Å between the centers of BPnDC ² -2 opposing phenyl rings, which is considered when the van der Waals surface is considered, 18.2 Fucked Skeletal body 1 formed 2D channels in the [100] and [010] directions.

The volume of solvent calculated by PLATON corresponds to 83.7%, 2.649 cm ³ g ^-1 . The density of 1 calculated after solvent removal dropped to 0.316 gcm ^-3 , which could be compared with the density of meso MOF-1 (0.262 gcm ^-3 ). Object molecules within the pores could not be purified because of the severe disorder common to microporous MOFs with large pores. Therefore, the presence and number of object molecules (8DMF and 6H ₂ O) in 1 were determined based on IR, basic analysis and TGA data. The final structural model was refined without object molecules by using PLATON's SQUEEZE option. Thermogravimetric analysis (TGA) for Skeletal 1 measured under N ₂ atmosphere shows that solvent object molecules are lost as soon as Crystal 1 is removed from the mother liquor. Heating to about 100 ° C. resulted in a decrease of 44.0% by weight (calculated. 45.8%). TGA and powder X-ray diffraction (PXRD) data measured at various temperatures suggest that 1 is thermally stable up to 230 ° C.

When 1 was heated in a Schlenk tube at 100 ° C. for 2 hours under vacuum, an undissolved solid [Cu ₂ (BPnDC) ₂ (bpy)] _n (1a) was produced. In FIG. 2, 1 and 1a are compared. The PXRD pattern of 1 is largely consistent with the simulation pattern derived from the X-ray single crystal raw data, which showed that the bulk sample was the same as the single crystal. However, using PLATON's SQUEEZE option was slightly different from the simulated pattern in which the electron density corresponding to the disordered object molecules was ignored. The PXRD pattern of the undissolved solid 1a is the same as the simulated pattern based on the sqeeze single crystal X-ray data of 1, indicating that the framework of 1 remains at 1a. When 1a was exposed to DMF vapor for 3 days, the PXRD pattern of 1 was regenerated, indicating that the object molecule was reintroduced back into the framework. Basic analysis data for resolvated samples showed 7 DMF and 4 water molecules per solid molecular formula (elemental analysis calcd (%) for {[Cu ₂ (BPnDC) ₂ (bpy)]? 7DMF 4H ₂ O} n : C 51.54, H 5.89, N 8.87; found: C 52.19, H 5.61, N 9.05).

1-2: {[Zn ₂ (BPnDC) ₂ (dabco)]? 13DMF? 3H ₂ O} n (2) X-ray structure and characteristics

Colorless crystals of ₂ were obtained by heating a DMF solution of Zn (NO ₃ ) ₂ ˜6H ₂ O, H ₂ BPnDC and 4-diazocyclo [2,2,2] octane at 100 ° C. for 3 days. lost. The X-ray structure of 1 was revealed by a non-transparent 3D coordination network similar to 1 (FIG. 3). The two Zn ^II centers at _{2 form} {Zn ₂ (O ₂ CR) ₄ } outer ring SBU units, but the nitrogen element of dabco, instead of 4,4'-bpy, is coordinated at the z-axis position of Zn ^II ions. . The Zn ^II --Zn ^II distance (3.0069 (15) suggests that there is no significant interaction between Zn ^II ions in the outer ring SBU (the sum of van der Waals of Zn ^II is 2.80 Å and Zn-O _BPnDC2- distance is average). and 2.040 (2) Å, and the Zn-N _dabco distance 2.038 (5) Å, and the angle is between two of the phenyl ring in the ^2- BPnDC is 59.02 (25) °, was less than 67.69 (14) ° 1. If between the adjacent rectangular unit formed by the carboxyl group carbon atoms of the outer ring SBUs each was 89.97 (1) °, and the outer ring are connected by SBUs BPnDC ^2- forms a 3D skeleton body axial position of the roller unit is a -., and b Along the axis, occupied by the nitrogen element of the dabco ligand.

As shown in FIG. 3, the framework 2 formed a channel having two kinds of triangular and hexagonal gaps. The effective lengths of the corner lengths and the small triangular channels were 8.0 and 3.9 mm 3, and the large hexagonal channels had 14.8 kW measured between the closest CCs of opposite phenyl rings of BPnDC ^2- . Considering the van der Waals surface area, the effective width of the hexagonal window was 11.4 mm 3. The free volume accessible by solvent molecules of 2 was 74.5% of the total crystal volume, as measured by PLATON. The voids were filled with object solvent molecules, but could not be purified by X-ray structure due to severe disorder. Therefore, the integrity and number of object molecules 13DMF and 3H2O at 2 were determined based on IR, basic analysis and TGA data. The final structural model Purified without object molecules by using PLATON's SQUEEZE option.

Skeletal 2 was insoluble in water and common organic solvents. Interestingly, when single crystal 2 was placed in organic solvents such as MeCN, MeOH, CHCl 3, toluene, benzene, acetone, hexane and diethyl ether, not only single crystals but also transparency were maintained. Thermogravimetric (TGA) showed that this synthesized material released solvent molecules even at room temperature and lost 52.4% weight when heated to 100 ° C. This corresponds to the loss of 13DMF and 3H 2 O molecules (calcd 56.3%). The powder X-ray diffraction pattern at various temperatures indicated that the skeletal structure of 2 could be maintained up to 360 ° C. (FIG. 4).

When 2 was heated in a Schlenk tube at 100 ° C. under vacuum for 2 hours, desolvated solid [Zn ₂ (BPnDC) ₂ (dabco)] n (2a) was produced. As shown in FIG. 5, the measured PXRD pattern of 2 closely matches the mock pattern obtained from the X-ray single crystal data, indicating that a large amount of samples is equivalent to a single crystal. The small difference in relative intensities between the measured and simulated patterns is due to the ignoring of the object molecules, since the simulated pattern applies PLATON's SQUEEZE option while the measured sample contains the object molecules. The PXRD pattern of the desolvated solid 2a was different from the pattern of 2, indicating that the skeletal structure changes with the removal of object molecules. However, the PXRD pattern of 2 was regenerated when 2a was exposed to DMF vapor for 3 days. This initial structure indicates that the object molecule is reintroduced and recovered. Basic analysis data for resolvated solids show that 12 DMF and 6 water molecules per molecule are contained in the solid. Elemental analysis (calculated) (%) of ({[Zn ₂ (BPnDC) ₂ (dabco)]? 12DMF? 6H ₂ O} n : C: 49.01, H 7.08, N 11.11; Elemental analysis (measured) : C 49.24, H 7.01, N 11.06) Unlike 1a, solid 2a does not absorb N ₂ or H ₂ gas, indicating that the material is non-porous for removal of object molecules. The type of linking molecule that connects the metal ions of the outer ring unit greatly affects the porosity of the material.

1-3: object transformation by divalent single crystal transformation with nucleic acid and single crystal

When single crystal 2 is dissolved in n-hexane for 3 days, 2 does not completely dissolve, and while maintaining transparency as well as single crystallinity, the DMF object molecules at 2 are exchanged with n-hexane, which is {[Zn ₂ ( BPnDC) ₂ (dabco)]-6 (n-hexane) -3H ₂ O} _n (2b) gave a single crystal and the X-ray crystal structure of 2b was determined. Object exchange was confirmed with large samples by basic analysis, FT-IR spectra and TGA data. TGA data of 2b indicated that the n-hexane molecules were released as soon as solid 2b was exposed to air and the water object molecules were heated to 140 ° C. to be removed. As shown in Figure 5, 2b loses n-hexane as soon as it is exposed to air, even if the PXRD pattern of 2b shows a broad peak, the simulated PXRD pattern of 2b was consistent with that of 2. After 2b exposure in air for several minutes, the PXRD pattern became different from either the measurement or simulation pattern for 2b. This indicates that the skeletal structure changes with the removal of the object molecule. The PXRD pattern measured for fully dried solid 2b was very similar to 2a. Furthermore, when the desolvated solid 2b was placed in n-hexane for 2 hours, the PXRD pattern of 2b could not be reproduced. This is because once the object molecule is removed, the original structure can hardly be recovered. The desolvated solid of 2b did not adsorb N2 or H2 gas.

The state of the X-ray data of 2b was as good as that of 2, and the cell parameters including the cell volume of 2b were mostly the same as those of 2, but the crystal space group was I41 / a compared to I 41 / amd of 2. Was changed (Table 1 and FIG. 6). The skeletal structure of 2b was compared with that of 2 in FIG. 3. The local structure of the Zn ₂ outer ring unit and BPnDC ^2- ligand was very similar to that of 2. However, Zn ₂ outer ring units and BPnDC ^2- ligands undergo positional and rotational rearrangements following object exchange. In particular, the back face angle between the phenyl ring linked to the carboxyl group forming outer ring SBUs was 9.02 (1.17) and 4.39 (1.03) ° at 2b, compared to 2.42 (1.22) of 2. Furthermore, the backside angle between the two phenyl rings of BPnDC ^2- changed from 59.02 (25) ° to 57.04 (27) °. As a result, the four carboxyl carbon atoms of each outer ring will bend, and the backside angle between the square planes of the outer ring units will be 50.84 (23) °, which is significantly different from 2 (89.97 (1) °). will be. In addition, the dabco ligand occupied at the axial position of the Zn ^II ion was more inclined with respect to the Zn--Zn axis. N-Zn-Zn: 174.08 (10) vs. 2 to 177.54 (13) °) This object response to a single crystal strain related to the motion of the molecular element can be applied to the design and development of sensors.

Experimental Example 2: [Cu ₂ (BPnDC) ₂ (bpy)] n (1a) gas adsorption capacity

2-1: Low Pressure Gas Adsorption Study

Gas adsorption-desorption experiments were carried out using an automated microporous gas analyzer Autosorb-1 or Autosorb-3B (Quantachrome Instruments). The synthesized crystal of 1 was introduced directly into the gas adsorption apparatus and the degassing process was performed by heating the sample at 100 ° C. for 2 hours under vacuum. All gases used were 99.999% pure and at each equilibrium pressure by static volume method, the N ₂ gas adsorption isotherms were measured at 77 K and 87 K, and the CO ₂ and CH ₄ gas adsorption isotherms were both 195 K and 273 K Measured in After the gas adsorption measurement, the sample weight was again accurately measured. Surface area and pore volume were determined from the N ₂ gas isotherm at 77 K. For multi-point Brunauer-Emmett-Teller (BET) and Langmuir surface area measurements, the data is P / P0 = 0.004-0.05 And P / P0 = 0.002-0.08.

2-2: high pressure H ₂  Gas adsorption measurement

A high pressure H ₂ adsorption isotherm of 1a was measured in the 0-70 bar range 77 K by gravimetric method using a Rubotherm magnetic suspension balance (MSB) instrument. Solid 1 was heated in a Schlenk tube at 100 ° C. for 2 hours under vacuum and an accurately measured amount of dried solid was introduced into the gas adsorption apparatus, which was removed at 25 ° C. under vacuum. All data were calibrated to take into account the buoyancy of the system and the sample. The sample density used in buoyancy correction was determined from the He substitution isotherm (up to 80 bar) measured at 298 K. The total storage capacity is the sum of the storage capacity due to the adsorption due to the adsorption of the surface area and the compression in the void of the adsorbent pores. The total amount of H ₂ adsorbed can be expressed as follows.

 2-3: H ₂  Measurement of isotherm heat of adsorption

An equivalent electronic heat of H ₂ adsorption was measured by a H ₂ absorption data measured at 1a of the 77 K and 87 K. A virial-type expresion was used in Equation 1, which consists of the ai and bi parameters, which are independent temperature. In Equation 1, P is the pressure, N is the amount of H ₂ gas adsorbed, T is the temperature, and m and n are the coefficients required to properly describe the isotherm.

(1)

(One)

In order to determine the value of the iso-electron column of the H2 adsorption, Equation 2 was applied, where R is the general gas constant.

(2)

(2)

2-4: [Cu ₂ (BPnDC) ₂ (bpy)] n (1a) gas adsorption capacity

In order to investigate 1a porosity, gas adsorption capacity for N ₂ , H ₂ , CO ₂ and CH ₄ gas was measured. N ₂ , H ₂ , CO ₂ and CH ₄ gas adsorption capacity of 1a is shown in Table 1.

The N ₂ adsorption isotherm of 1a shows permanent porosity and shows a typical Type-I adsorption morphology (FIG. 7). Brunauer-Emmett-Teller (BET) and Langmuir surface areas were 2585 and 2914 m ² g ^{- 1} , which is the value of IRMOF-1 (2833m ² g ^-1 ) Can be compared with The pore volume measured by the Dubinin-Radushkevich equation was 1.047 cm ³ g ^-1 . The development of pore size distribution based on the Sait o-Foley (SF) model (A. Saito, HC Foley, AIChE J. 1991 , 37, 429-436.) Showed that the pore diameters of 1a were 14.0 and 18.2. .

Solid 1a adsorbs up to 1.68% by weight of H ₂ gas at 77 K and 1 atm (187 cm ³ g ^-1 at STP, 6.85 H ₂ molecules per formula unit, cal culated H ₂ density: 0.016 gcm ^-3 ), 87 Adsorbed up to 1.10 wt% in K and 1 atm (122 cm ³ g ^-1 at STP, 4.45 H ₂ molecules per formula unit). The H ₂ adsorption capacity of 1a was relatively good and could be compared with the value of [Zn ₂ (tmbdc) ₂ (bpy)] (1.68 wt% at 78 K and 1 atm). Where tmbdc is tetramethylterephthalate. As with the irregularities alsik measured from the H ₂ isotherms at 77 K and 87 K, an equivalent electronic heat of H ₂ adsorption capacity of the 1a, 7.98-6.43 kJmol according to the degree of loading H ₂ ^{- 1.} Equivalent electron rows in this range (7.98 kJmol ^-1 ) are those of desolvated Cu ₃ [(Cu ₄ Cl) ₃ (TPB-3tz) ₈ ] ₂ -11CuCl ₂ -8H ₂ O -120DMF solids (8.2 kJmol ^-1) ) Can be compared.

When the H ₂ pressure increased from 77 K to 70 bar, adsorption exceeded 4.87 wt%. Considering the crystallographic density of the sample and the skeletal density measured through He, the total amount of H ₂ adsorption of 1a was 10.0% by weight at 70 bar and 77 K. The big difference between excess adsorption and total H ₂ adsorption is due to the large free space (77.4%) of the sample. After 1a exposure in air for 3 days, even though the H ₂ adsorption capacity of some MOF materials was dependent on the degree of air exposure, the adsorption capacity of H ₂ remained still in the reactivation state.

The CO ₂ gas adsorption isotherms of 1a measured at 195 K and 273 K are shown in FIG. 8. The isotherm of CO ₂ at 195 K showed two stages of adsorption with small hysteresis. In the initial step, 1a is 37.3% by weight of CO ₂ in ^{0.15atm (8.5 mmolg -1, 190 cm} 3 g -1 at STP) for adsorption, and 113.8% by weight in 0.151atm area at the second step (25.8 mmolg ^-1, 579 cm ³ g ^-1 at STP). Aberration hysteresis, pressure-dependent gas adsorption, has been observed in several flexible and dynamic pore MOFs that respond to specific object molecules through breathing or door opening processes. The Yaghi group recently reported an S-type CO ₂ isotherm for IRMPF-1, which is similar to its current state, and was explained by the attraction electrostatic interaction between CO ₂ molecules. The CO ₂ adsorption capacity of 1a was more pronounced than other MOFs measured under similar conditions. The highest adsorption data reported so far is 148.9 wt% in IRMO F-1. 273 K and 1a of the CO ₂ storage capability 11.0% by weight of at ^{1atm (2.5 mmolg -1, 56.0 cm} 3 g -1 at STP) , and which is significantly lower than the one measured at 195 K.

1a of the CH ₄ gas isotherms 195 7.27% by weight of K and at ^{_{1 atm CH 4 (4.53 mmolg -1}} , 101.5 cm 3 g -1 at STP) until, at 273 K and 1 m in a 1.11 wt% (0.69 mmolg ^{- 1} , 15.5 cm ³ g ^-1 at STP). The big difference between the adsorption capacity of CO ₂ and CH ₄ at 1a is that it can be applied to gas separation processes.

Table 1 shows the gas adsorption data of 1a.

gas T (K) Surface area of 1a (m ^-1 g ^-1 ) ^{[a], [b]} Pore volume of 1a (cm ³ g ^-1 ) Mmol of gas per gram of 1a % By weight gas ^[c] G of gas per volume of 1a N ₂ 77 2914 ^[a] , 2585 ^[b] 1.047 31.3 87.7 277 H ₂ 77 8.3 1.68 5.31 24.2 ^[e] 4.87 ^[e] 15.4 ^[e] 49.6 ^[f] 10.0 ^[f] 31.6 ^[f] H ₂ 87 5.4 1.10 3.48 CO ₂ 195 25.8 113.8 360 CO ₂ 273 2.5 11.0 34.8 CH ₄ 195 4.5 7.3 23.1 CH ₄ 273 0.7 1.1 3.6

[a] Langmuir surface area

[b] BET surface area

[c] amount of adsorbed gas; P = 690 Torr in N ₂ and P = 760 Torr in other gases

[d] Weight of adsorbed gas / gx Density of sample (density: 316 gL ⁻¹ ). However, it is assumed that the unit volume of 1a is equal to 1.

[e] excess adsorption at 77 K and 70 bar

[f] Total adsorption at 77 K and 70 bar

FIG. 1 shows the X-ray crystal structure of 1. FIG. a) Coordination shape in outer ring Cu ₂ (BPnDC) ₂ (bpy) units. 4,4'-bpy turns into two layers and becomes disordered. Here, H atoms are omitted for clarity. Cu is yellow, N is blue, O is red, C is pink, and C in 4,4'-bpy is light blue. b) The arrangement of outer ring SBUs in the framework. Outer ring SBUs are located at an adjacent outer ring square and 90.00 (0) ° back angle. c) how the outer ring SBUs are located in constructing 3D network {Cu ₂ (BPnDC) ₂ }. The outer ring square surfaces of (S1 and S5), (S2, S4, S6 and S8) and (S3 and S7) extend along the a- (green), b- (pink) and c-axis (yellow). d) shows how the 4,4'-bpy linker in c is linked to the outer ring unit of the network. e) The CPK shape represents two kinds of channels.

2 shows the PXRD pattern of 1. a) 1 synthesized; b) simulated pattern based on single crystal X-ray raw data of 1; c) simulated pattern based on single crystal X-ray raw data of 1, with the electron density of disordered object molecules removed by PLATON's SQUEEZ option; d) 1a prepared by drying 1 for 1 hour at 100 ° C. under vacuum; e) solid separated after exposing 1a to DMF vapor for 3 days.

 3 is an X-ray crystal structure of 2 and 2b. A) 2 and b) 2b show the side arrangement of the outer ring SBUs. The upper surface shows two kinds of channels in c) 2 and d) 2b.

4 is a PXRD pattern of 2 measured at various temperatures.

Fig. 5 is a PXRD pattern. (A) Synthesized PXRD pattern of 2 (b) Simulated PXRD pattern of 2 single crystal X-ray data of which electron density of disordered object molecule is removed by PLATON SQUEEZ option (c) Vacuum Measurement pattern of 2a prepared by drying 2 at 100 ° C. for 2 hours (d) Measurement pattern of solid separated after 2a exposure to DMF vapor for 3 days (e) Object-exchange solid, {[Zn ₂ (BnXDC) ₂ (dabco)]? (N-hexane)? H ₂ O} _n (2b) Measurement pattern (f) 2b X-ray single crystal from which electron density of disordered object molecules was removed by PLATON's SQUEEZ option Simulation pattern based on data (g) Measurement pattern of solid after exposing 2b in air for 5 minutes (h) Measurement pattern of solid obtained by drying 2b at 150 ° C. for 2 hours under vacuum (i) n − for 2 days Measurement pattern of solid obtained after putting a sample of (g) in hexane

FIG. 6 is a crystal photograph of 2 and 2b.

7 is a gas adsorption isotherm. a) N2 adsorption curve measured at 77 K; Po (N ₂ ) = 804.00 Torr; Distribution of inside pore size b) 77 K (W), and 87 a H c measured at K (triangle)), such as an array of H ₂ adsorption d) greater than (W) and the total (triangular, crystallographic density and cheukjeok a skeleton with He Considering density) H ₂ adsorption at 77 K and high pressure; Filled circle: adsorption, open circle: desorption

FIG. 8 shows 195 K (circle) and 273 K (square) CO ₂ (pink) and CH ₄ (violet) adsorption isotherms, where the filled circle represents adsorption and the open circle shows desorption.

Claims (15)

As a metal-organic skeleton or a solvate thereof represented by the following Chemical Formula 1: [Formula 1] {[M ₂ (L1) ₂ (L2)] X (Sol1)? Y (Sol2)} _n M is any one selected from the group consisting of Cu, Zn, Cd, Ni, Co, Mn, Ca and Mg; L1 is BPnDC, bis (4-carboxyphenyl) methane, N, N-bis (4-carboxyphenyl) amine, 1,1-bis (4-carboxyphenyl) ethylene and 4,4'-oxybis (benzoic acid) Any one selected from the group consisting of; L2 is pyrazine, 4,4'-bipyridine, 4-diazabicyclo [2,2,2] octane, trans-1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridine) Dill) ethane, 1,3-bis (4-pyridyl) propane, 3,6-bis (4-pyridyl) -1,2,4,5-tetrazine, 4,4`-azodipyridyl and Any one selected from the group consisting of 4,4′-dipyridylamine; Sol1 and Sol2 are methanol, ethanol, butanol, acetonitrile, methylene chloride, chloroform, toluene, benzene, acetone, n-hexane, dodecane, THF, ether, water, dioxane, pyridine, DEF, DMA, DEA and DMF Any one selected from the group consisting of; X and Y are each an integer from 0-20; n is an integer of 1 or more; The metal organic framework of [Formula 1] has a Langmuir surface area of 2 000-4500 m ² g ⁻¹ , BET surface area of 1500-3500 m ² g ^−1, and Dubinin-Radschkevic pore volume of 0.3- 3.0 cm ³ g ^-1 , total free space is 70-95%, has an equi ^- arrangement of 5-12 kJmol ^-1 , pore size is 8-30 mm, and hydrogen adsorption capacity is 4% by weight at 77 K and 70 bar And a carbon dioxide adsorption capacity of 100 wt% or more at 1 95 K and 1 atm. 3D non-penetrating porous mixed-ligand metal-organic framework. The method of claim 1, wherein M of the metal organic framework of [Formula 1] is any one selected from the group consisting of Cu, Zn, Cd, Ni, and Co; L 1 is any one selected from the group consisting of BPnDC, bis (4-carboxyphenyl) methane, N, N-bis (4-carboxyphenyl) amine and 1,1-bis (4-carboxyphenyl) ethylene; L2 is 4,4'-bipyridine, 4-diazocycle [2,2,2] octane, trans-1,2-bis (4-pyridyl) ethylene and 1, 2-bis (4-pyridyl) Ethane is any one selected from the group consisting of; Sol is a metal-organic skeleton, characterized in that any one selected from the group consisting of ethanol, butanol, toluene, n-hexane, THF, water and DMF.  According to claim 1, It is any one selected from the group consisting of Cu, Zn, Cd, Ni and Co of the metal organic skeleton of [Formula 1]; When M is Cu, L 1 is BPnDC, L 2 is 4,4′-bipyridine, Sol 1 is DMF, and Sol 2 is water; When M is Zn, L 1 is BPnDC, L 2 is 4-diazabicyclo [2,2,2] octane, Sol 1 is DMF or n-hexane, and Sol 2 is water; L1 is bis (4-carboxyphenyl) methane when M is Ni, L2 is trans-1,2-bis (4-pyridyl) ethylene, Sol1 is butanol, and Sol2 is water; L1 is N, N-bis (4-carboxyphenyl) amine when M is Cd, L2 is 1,2-bis (4-pyridyl) ethane, Sol1 is THF, and Sol2 is ethanol; When M is Co, L1 is 1,1-bis (4-carboxyphenyl) ethylene, L2 is 4,4'-bipyridine, Sol1 is n-hexane, Sol2 is toluene Skeletal body. delete [Claim 2] The metal-organic skeleton of [Formula 2] according to claim 1, wherein the solvate of [Formula 1] is prepared by heating and desolvating for 1-4 hours under vacuum at 80-120 ° C. [Formula 2] [M ₂ (L1) ₂ (L2)] _n N is the same as defined in claim 1. The metal-organic skeleton of claim 1, wherein the metal-organic skeleton of [Formula 1] is represented by the following [Formula 3]. (3) [Cu ₂ (BPnDC) ₂ (bpy)] _n N is the same as defined in claim 1. According to claim 6, wherein the metal-organic skeleton of [Formula 3] Langmuir surface area is 2500-3500 m ² g ^{- 1} , BET surface area is 2000-3000 m ² g ^-1 , Dubinin-Radsuke Beach void volume is 0.5-2.0 cm ³ g ^-1 , total free space is 75-90%, has an equi ^- arrangement of 6-10 kJmol ^-1 and pore size is 10-25 ,, A metal-organic framework characterized in that the hydrogen adsorption capacity is at least 4% by weight at 77 K and 70 bar, and the carbon dioxide adsorption capacity is at least 110% by weight at 195 K and 1 atm. The method according to claim 7, wherein the metal-organic skeleton of [Chemical Formula 3] is prepared by heating the solvate of [Chemical Formula 4] for 1-4 hours under vacuum at 80-120 ° C. for desolvation. Metal-organic frameworks. [Formula 4] {[Cu ₂ (BPnDC) ₂ (bpy)]? 8DMF? 6H ₂ O} _n N is the same as defined in claim 1. According to claim 1, wherein the metal-organic skeleton of [Formula 1] is represented by the following [Formula 5], the total free space is 70-85%, characterized in that the pore size is 5-15- Organic framework. [Chemical Formula 5] {[Zn ₂ (BPnDC) ₂ (dabco)]? 6 (n-hexane)? 3H ₂ O} _n N is the same as defined in claim 1. The metal-organic framework of claim 9, wherein the metal-organic framework of [Formula 5] is prepared by exchanging DMF of [Formula 6] with n-hexane. [Formula 6] {[Zn ₂ (BPnDC) ₂ (dabco)]? 13DMF? 3H ₂ O} _n N is the same as defined in claim 1. delete delete delete delete A gas apparatus comprising the metal-organic framework according to any one of claims 1 to 3 and 5 to 10 and selected from a gas sensor device, a gas reservoir, and a gas separation device.

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