SYNTHESIS OF METAL ORGANIC FRAMEWORK (MOF) MATERIALS WITH HIGH ADSORPTION CAPACITY OF ORGANIC COMPOUNDS AND CO2 CAPTURE

Abstract

Metal-organic framework material (MOF), comprising at least one metal center and at least one organic compound selected among the compounds according to formula (I):

##STR00001##

wherein n is from 1 to 2, R is (CH.sub.2CH.sub.2O).sub.mCH.sub.3 with m from 1 to 7; preferably when n=1, the two COOH groups are located in the para position relatively to the aryl substituted by the two RO groups; and preferably when n=2, the four COOH groups are located in the meta position relatively to the aryl substituted by the two RO groups.

Claims

1. Organic compound for the preparation of a MOF, said organic compound being selected among the compounds according to formula (I): ##STR00020## wherein n is from 1 to 2, R is (CH.sub.2CH.sub.2O).sub.mCH.sub.3 with m from 1 to 7; preferably when n=1, the two COOH groups are located in the para position relatively to the aryl substituted by the two RO groups; and preferably when n=2, the four COOH groups are located in the meta position relatively to the aryl substituted by the two RO groups.

2. Organic compound according to claim 1, wherein n is 2; the organic compound being selected among the compounds according to formula (II): ##STR00021##

3. Organic compound according to claim 2, wherein m is less than 4.

4. Metal-organic framework material (MOF), comprising at least one metal center and at least one organic compound according to claim 1.

5. Metal-organic framework material according to claim 4, wherein the metal center of the hydrophobic core is selected from Li, Na, Rb, Mg, Ca, Sr, Ba, Sc, Ti, Zr, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Ni, Pd, Pt, Cu, Au, Zn, Al, Ga, In, Si, Ge, Sn, Bi, Cd, Mn, Tb, Gd, Ce, La, or Cr, and preferably Cu, Zn, Zr, Ca or Mg.

6. Metal-organic framework material according to claim 5, wherein the organic compound is: ##STR00022## and the metal center is selected from Cu, Zn, Mg, Ni and Ca.

7. Metal-organic framework material according to claim 5, wherein the organic compound is selected among: ##STR00023## and the metal center is selected from Cu, Zn, Mg, Ni and Ca.

8. Metal-organic framework material according to claim 4, wherein the organic compound is: ##STR00024## and the metal center is selected from Cu, Zr, Zn, Fe and Ca.

9. Use of a MOF according to 8 claim 4, for the adsorption of volatile organic compounds (VOCs), and preferably for the adsorption of acetic acid or aldehydes.

10. Use of a MOF according to claim 4, for the decontamination of aqueous solutions containing organic pollutants such as dyes and pharmaceutical compounds, and preferably for the adsorption of a dye, preferably selected among a cationic and an anionic dye, and most preferably selected among at least methylene blue and alizarin yellow R.

11. Use of a MOF according to claim 4, for the adsorption of a gas, preferably selected among methane, hydrogen, acetylene, nitrogen, and CO.sub.2, most preferably CO.sub.2.

12. Use of a MOF according to claim 11, for the adsorption of CO.sub.2 wherein the concentration of adsorbed gas is greater than 17 mmol/g at 10 bars, and 0 C.

13. Preparation method for the synthesis of a MOF according to claim 4, wherein the metal center is Cu, and the MOF is prepared by the dissolution of the organic compound, in a DMF/water mixture, followed by an addition plus dissolution of Cu(NO.sub.3).sub.2.3H.sub.2O into the reaction mixture, the reaction mixture is left at 70-90 C. during several hours.

14. Preparation method for the synthesis of the organic compound according to claim 1, comprising the steps of: aactivating phenol groups of a hydroquinone bearing two halogen or two -OTf; groups; bperforming a Suzuki-Miyaura reaction to replace halogen and/or -OTf by aryl groups bearing protected acid acetic substituents; and cdeprotecting the acid acetic substituents; preferably according to the following synthetic pathway: ##STR00025##

15. Preparation method according to claim 14, wherein X=Br; G=Ts and the first step of the synthetic pathway is realized in DMF at 80 C., and the Suzuki-Miyaura coupling reaction step is performed according to: ##STR00026##

Description

DETAILED DESCRIPTION OF CERTAIN PREFERRED EMBODIMENTS OF THE INVENTION

Analysis and Experimental Protocols

[0040] .sup.1H-NMR and .sup.13C-NMR spectra were recorded at 25 C. on Brucker AV300 (300 MHZ) Bruker AV400 (400 MHZ) or Bruker AV500 (500 MHz) spectrometers in deuterated solvents with the residual solvent peak used as the internal reference (CDCl.sub.3: 7.26 ppm for .sup.1H, 77.2 ppm for .sup.13C; DMSO-d6: 2.50 ppm for 1H, 49.9 ppm for .sup.13C). The abbreviations for specifying the multiplicity of 1H-NMR signals are defined as follows: s=singlet, d=doublet, dd=doublet of doublet, ddd=doublet of doublet of doublets, t=triplet, q=quadruplet, m=multiplet, br=broad. Coupling constants are given in Hertz and chemical shifts in ppm.

[0041] MS (Mass spectrometry) was performed at the Service de Spectromtrie de Masse of the University of Strasbourg. Low (LRMS) (positive and negative mode ESI: Electro Spray lonization) were recorded on Thermoquest AQA Navigator with time flight detector.

[0042] Elemental analyses were performed on a Thermo Scientific Flash 2000 by the Service Commun de Microanalyse of the University of Strasbourg.

[0043] UV-Vis spectrometry measurements were performed on a Perkin-Elmer Lambda 900 spectrophotometer in 1 mm quartz cuvettes. Wavelength (A) are given in nm. All solvents used were purchased as spectrometric grades.

[0044] Thermo gravimetric analysis (TGA) were performed on a Pyris 6 TGA Lab System apparatus (Perkin-Elmer), using a N.sub.2 flow of 20 mL/min and a heat rate of 5/min.

[0045] X-Ray diffraction: Single-crystal data were collected on a Bruker SMART CCD diffractometer with Mo-K radiation at 173 K. The structures were solved using SHELXS-97 and refined by full matrix least-squares on F2 using SHELXL-2014 with anisotropic thermal parameters for all non-hydrogen atoms.

[0046] The hydrogen atoms were introduced at calculated positions and not refined (riding model). The SQUEEZE command has been employed when disordered solvent molecules were present in structures, to account for the corresponding electron density.

[0047] XRPD Diffraction patterns: Powder X-ray diffraction (XRPD) data were recorded using a Bruker D8 AV diffractometer with Cu-K radiation at room temperature. The radiation wavelength of the incident X-rays was 1,54 and a 20 range is from 4 to 40 was investigated.

[0048] BET measurements: Nitrogen adsorption-desorption isotherms were measured at 77K up to 1 bar using the ASAP 2020 Micromeritics analyzer. Carbon dioxide adsorption-desorption isotherms up to 10 bars at 273K were performed by using ASAP 2050 Micromeritics analyzer.

[0049] The preparation of compounds 1 and 2 were realized according to protocols detailed in [3].

Synthesis and Characterization of Organic Compounds Used as Ligands in the MOF:

[0050] The preparation of the different organic compounds according to formula (II) was performed according to the scheme reported on FIG. 1. [0051] Preparation of TsO (CH.sub.2CH.sub.2O)CH.sub.3, TsO(CH.sub.2CH.sub.2O).sub.2CH.sub.3, TsO(CH.sub.2CH.sub.2O).sub.3CH.sub.3, or TsO(CH.sub.2CH.sub.2O).sub.7CH.sub.3: (for TsO(CH.sub.2CH.sub.2O).sub.2CH.sub.3, applicable for all) Double necked flask dried oven before reaction. 2-(2-(2-methoxyethoxy) ethoxy) ethanol (9.9 mmol) dissolved in THF (20 mL) and water (15 mL) with NaOH (30 mmol). Later, tosyl chloride (10.5 mmol) dissolved in THF (20 mL) and added dropwise to the mixture while mixing at ambient temperature. Despite THF and water are miscible, in our case (most probably because of NaOH) the layers were separated. After overnight reaction, layers separated. Aqueous layer washed with 2 times with diethyl ether and once with dichloromethane. Organic layer washed twice with water. Organic layers combined, dried on MgSO.sub.4 filtered with cotton and reduced. Pale yellow oil obtained. Yield: 61%.

[0052] Alternative method: Double necked flask dried oven before reaction. In an ice bath, 2-(2-methoxyethoxy) ethanol (22 mmol) dissolved in CH.sub.2Cl.sub.2 under Argon atmosphere.

[0053] Further, triethyleneamine (22 mmol) poured to the flask. In a separate flask tosyl chloride (23 mmol) dissolved in CH.sub.2Cl.sub.2, white cloudy solution obtained. The solution of tosyl chloride added dropwise to mixture. Reaction continued overnight (18 h). 50 ml water poured to reaction mixture. Aqueous phase washed with dichloromethane, organic phase collected and washed with 3 M HCl (50 ml), NaHCO.sub.3 (50 ml) and with water (50 ml). Dried on MgSO.sub.4, filtered and reduced.

[0054] Pale yellow oil obtained and purified further with column (CH.sub.2Cl.sub.2/cyclohexane 1/1). Yield of compounds: 80%

[0055] Preparation of compounds 1 or 2 or 7: TsO(CH.sub.2CH.sub.2O)CH.sub.3 or TsO(CH.sub.2CH.sub.2O).sub.2CH.sub.3 (11.22 mmol), dibromohydroquinone (4.48 mmol), and potassium carbonate (26.88mmol) were placed in a double necked bottom flask under inert atmosphere (Ar), and DMF solvent was added. The mixture was stirred overnight (18 h) at 80 C., then the reaction mixture was quenched with 120 ml water to obtain a white precipitate. Small amount of benzoquinone gives brownish color. The product was recrystallized to eliminate this color. Yield for compound 1=53,6%. Compound 2=71%. Compound 7=70%.

##STR00011##

Alternative Preparation Method for Compound 7:

[0056] Double necked flask dried oven before reaction. Dibromohydroquinone (0.25 mmol), compound 3 (0.75 mmol) and potassium carbonate (1 mmol) added to flask. In presence of acetone (50 mL). Then flask evacuated and filled 2 times with Argon. Reaction mixture heated to reflux and gently evacuated and filled 2 times with Argon. The one of the key points of this reaction is prevent the formation of benzoquinone which gives red color to the product even at trace amounts and decreases the yield of the reaction. After 2 days reaction, reaction mixture dried, some water, methanol and excess NaOH added and heated to 50 C. for 5 min while mixing. Later, methanol evaporated, aqueous layer washed twice with diethyl ether. Organic layers combined and washed twice with water. Dried on MgSO4, filtered and reduced. Yield for compound 7: 63%.

Preparation of Compound 8:

[0057] Firstly, dimethyl 5-bromo-benzene-1,3-dicarboxylate (5.4 g, 20 mmol) tared on a triple necked round bottom flask. Under Ar atmosphere, bis-(pinacolato) diborane (6 g, 23.6 mmol) and potassium acetate (oven dried) (5.6 g, 57 mmol) added respectively. Then, dry 1,4-dioxane (50 ml) poured and solution degassed with Ar for 5 min. Finally, Pd(dpff)2Cl2 (0.2 g, 0.27 mmol) added and mixture heated to 80 C. After 24 h reaction stopped and the mixture extracted with ethyl acetate (20 ml). Organic layer dried over MgSO.sub.4, filtered and reduced at vacuum. Obtained crude product purified with column (silica gel, ethyl acetate/petroleum ether, 1/8 v:v). White powder obtained with 85% yield (5.427 g, 17 mmol).

##STR00012##

Preparation of Compound 9:

[0058] In a 100 mL flask 3,5-Dimethylphenylboronic acid (3.33 mmol) dissolved in t-BuOH/water (20/15 mL). Later, NaOH (10 mmol) added and mixture heated to reflux. KMnO.sub.4 (27 mmol) added portion wise. After overnight reaction, mixture filtered, t-BuOH evaporated, and acidified. Product filtered and fast rinsed with acetone. Snow white powder obtained. Yield: 60%.

##STR00013##

[0059] Preparation of compounds 3 or 4: The dimethyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) isophthalate (6.25 mmol) and compound 1 or 2 (2.08 mmol) were placed in a double necked bottom flask, then 40 ml DMF was added under Argon atmosphere. After 20 min mixing under argon, cesium carbonate (6.25 mmol) and tetrakis (triphenylphosphine) palladium (0) (0.054 mmol) were added, and the mixture was heated under stirring. Reaction continued overnight. Reaction mixture was then dried under reduced pressue, extracted with chloroform, and purified with column. A white solid was obtained.

Compound 3: Yield=79%;

[0060] .sup.1H NMR (500 MHZ, CDCl.sub.3) 8.67 (d, J=1.7 Hz, 2H), 8.49 (d, J=1.7 Hz, 4H), 7.07 (s, 2H), 4.13 (t, J=4.7 Hz, 4H), 3.98 (s, 12H), 3.66 (t, J=4.7 Hz, 4H), 3.34 (s, 6H); .sup.13C NMR (126 MHZ, CDCl.sub.3) 166.38, 150.39, 138.61, 134.90, 130.47, 129.71, 129.44, 116.28, 71.01, 69.32, 59.23, 52.47;

[0061] LRMS (ESI.sup.+) calculated: C.sub.32H.sub.34O.sub.12, 610.21 found: C.sub.32H.sub.34O.sub.12Na, 633.19; elemental analysis (%) for C.sub.32H.sub.34O.sub.12 calculated: C 62.95, H 5.61; found: C 60.52, H 5.54

Compound 4: Yield=90%;

[0062] .sup.1H NMR (500 MHZ, CDCl.sub.3) 8.64 (t, J=1.7 Hz, 2H), 8.44 (d, J=1.7 Hz, 4H), 7.02 (s, 2H), 4.12 (t, J=4.9 Hz, 4H), 3.96 (s, 13H), 3.74 (t, J=4.9 Hz, 4H), 3.58-3.53 (m, 4H), 3.46-3.41 (m, 4H), 3.29 (s, 6H).

[0063] .sup.13C NMR (126 MHz, CDCl.sub.3) 166.32, 150.28, 138.69, 134.88, 130.45, 129.65, 129.40, 116.06, 71.88, 70.79, 69.68, 69.42, 59.02, 52.47.

[0064] LRMS (ESI.sup.+) calculated: C.sub.36H.sub.42O.sub.14, 698.26, found C.sub.36H.sub.42O.sub.14Na, 721.25; elemental analysis (%) for calculated: C 61.88, H 6.06; found C 58.95, H 5.82.

[0065] Preparation of compounds 5 or 6: compound 3 or 4 (1.64 mmol) was dissolved in the mixture of 100 ml THF and 100 ml aq. KOH (2M). The mixture was heated to 90 C. overnight. The heating was stopped, and once reaction mixture reached RT, THF was evaporated under reduced pressure. The aqueous solution was treated with 6M HCl to pH1. The obtained precipitate was filtered and washed with water, plus dried under vacuum overnight.

[0066] Compound 5: Yield=89%;

[0067] .sup.1H NMR (300 MHZ, DMSO) : 13.29 (s, 4H), 8.46 (t, J=1.6 Hz, 2H), 8.42 (d, J=1.6 Hz, 4H), 7.25 (s, 2H), 4.24-4.15 (m, 4H), 3.63-3.54 (m, 4H), 3.22 (s, 6H); .sup.13C NMR (126 MHZ, DMSO) : 167.12, 150.23, 138.70, 134.67, 131.67, 129.22, 129.08, 116.25, 70.93, 69.07, 58.68;

[0068] LRMS (ESI+) calculated: C28H26012,554.14 found: C28H26012, 553.14; elemental analysis (%) for C28H26012 calculated: C 60.65, H 4.46; found: C 52.46, H 4.73.

Compound 6: Yield=95%;

[0069] .sup.1H NMR (500 MHZ, DMSO) 13.31 (s, 4H), 8.45 (t, J=1.7 Hz, 2H), 8.38 (d, J=1.6 Hz, 4H), 7.23 (s, 2H), 4.20-4.15 (m, 4H), 3.67-3.62 (m, 4H), 3.46 (dd, J=5.8, 3.8 Hz, 4H), 3.33 (d, J=2.1 Hz, 4H), 3.14 (s, 6H);

[0070] .sup.13C NMR (126 MHZ, DMSO) 167.13, 150.24, 138.75, 134.66, 131.62, 129.33, 129.07, 116.33, 71.60, 70.18, 69.48, 69.46, 58.37;

[0071] LRMS (ESI.sup.+) calculated: C.sub.32H.sub.34O.sub.14 642.19 found: C.sub.32H.sub.34O.sub.14K 681.16 (one K atom plus) elemental analysis (%) for C.sub.32H.sub.34O.sub.14 calculated: C 59.81, H 5.33; found: C 58.13, H 5.18.

[0072] Preparation of compound 10 (general method applicable to all final ligands): : Double necked flask dried oven before reaction. Compound 7 (0.107 mmol) and compound 9 (0.24 mmol) tared, then 10 ml ethanol and 5 ml water added under Argon atmosphere. After 20 min mixing under argon, Potassium carbonate (0.47 mmol) and Tetrakis (triphenylphosphine) palladium (0) (0.017 mmol) added and mixture refluxed. Reaction continued overnight.

[0073] Reaction mixture filtered over celite. Ethanol from the mixture is evaporated, later some water added following by acidification with concentrated HCl. White slightly yellow solid filtered and rinsed with water and acetone. Yield for compound 10: 52%,

##STR00014##

[0074] .sup.1H NMR (300 MHZ, DMSO) 8.45 (t, J=1.6 Hz, 2H), 8.38 (d, J=1.6 Hz, 4H), 7.23 (s, 2H), 4.17 (dd, J=4.2, 2.2 Hz, 4H), 3.66 (dd, J=5.4, 3.7 Hz, 4H), 3.47-3.45 (m, 4H), 3.38 (d, J=1.0 Hz, 4H), 3.33 (d, J=2.5 Hz, 4H), 3.31 (d, J=1.2 Hz, 4H), 3.17 (s, 6H).

[0075] .sup.13C NMR (126 MHZ, DMSO) 167.10, 150.22, 138.76, 134.67, 131.63, 129.28, 129.07, 116.30, 71.61, 70.39, 70.12, 69.92, 69.47, 69.41, 58.42.

[0076] LRMS (ESI.sup.+) for compound 10 calculated: C.sub.36H.sub.42O.sub.16, 730.25; found: C.sub.36H.sub.41O.sub.16, 729.24 Elemental analysis (%) for C36H42016 calculated: C 59.17, H 5.79; found: C 57.39, H 5.63.

[0077] Preparation of compounds 11, 12 and 13 (general method applicable to compounds 11-13):

[0078] Double necked flask dried oven before reaction. Compound 1 or 2 or 7 (1 eq) and 4-carboxyphenylboronic acid (3 eq) tared, then ethanol and water added (2/1: V/V) under Argon atmosphere. After 20 min mixing under argon, Potassium carbonate (6 eq) and Tetrakis (triphenylphosphine) palladium (0) (0.1 eq) added and mixture refluxed. Reaction continued overnight.

[0079] Reaction mixture filtered over celite. Ethanol from the mixture is evaporated, later some water added following by acidification with concentrated HCl. White slightly brown solid filtered and rinsed with water, acetone and diethyl ether. Yield for compound 11: 89%, compound 12: 68%, compound 13: 80%.

##STR00015##

[0080] .sup.1H NMR (500 MHZ, DMSO): 12.97 (s, 2H), 8.01-7.96 (m, 4H), 7.78 (d, J=8.3 Hz, 4H), 7.15 (s, 2H), 4.19-4.14 (m, 4H), 3.63-3.57 (m, 4H), 3.25 (s, 6H).

[0081] .sup.13C NMR (126 MHZ, DMSO): 167.24, 149.80, 142.04, 129.55, 129.42, 129.25, 128.98, 115.93, 70.49, 68.44, 58.23.

[0082] LRMS (ESI.sup.+) for compound 11 calculated: C.sub.26H.sub.26O.sub.8, 466.16; found: C.sub.26H.sub.25O.sub.8, 465.16Elemental analysis (%) for C.sub.26H.sub.26O.sub.8 calculated: C 66.94, H 5.62; found: C 62.88, H 5.30.

##STR00016##

[0083] .sup.1H NMR (500 MHZ, DMSO): 12.96 (s, 2H), 8.02-7.96 (m, 4H), 7.84-7.78 (m, 4H), 7.17 (s, 2H), 4.20-4.14 (m, 4H), 3.71-3.64 (m, 4H), 3.55-3.49 (m, 4H), 3.44-3.39 (m, 4H), 3.21 (s, 6H).

[0084] .sup.13C NMR (126 MHZ, DMSO): 67.17, 149.70, 141.94, 129.51, 129.29, 129.11, 128.88, 115.80, 71.26, 69.61, 68.88, 68.50, 57.99.

[0085] LRMS (ESI.sup.+) for compound 12 calculated: C.sub.30H.sub.34O.sub.10, 554.22; found: C.sub.30H.sub.34O.sub.10K, 593.18 Elemental analysis (%) for C.sub.30H.sub.34O.sub.10 calculated: C 64.97, H 6.18; found: C 64.67, H 6.04.

##STR00017##

[0086] .sup.1H NMR (500 MHZ, DMSO): 12.90 (s, 2H), 7.98 (dd, J=8.4, 1.6 Hz, 4H), 7.79 (dd, J=8.3, 1.8 Hz, 4H), 7.16 (s, 2H), 4.17 (dd, J=5.8, 3.4 Hz, 4H), 3.72-3.66 (m, 4H), 3.53-3.51 (m, 4H), 3.50-3.48 (m, 4H), 3.47 (dd, J=5.7, 3.7 Hz, 4H), 3.39-3.38 (m, 4H), 3.19 (s, 6H). (Because of water molecule peaks were slightly mixed)

[0087] .sup.13C NMR (126 MHz, DMSO): 167.76, 150.21, 131.92, 129.99, 129.82, 129.41, 129.20, 116.30, 71.70, 70.37, 70.32, 70.06, 69.43, 69.01, 58.48.

[0088] LRMS (ESI.sup.+) for compound 13 calculated: C.sub.34H.sub.42O.sub.12 642.27; found: C.sub.34H.sub.41O.sub.12, 641.26 Elemental analysis (%) for C.sub.34H.sub.42O.sub.12 calculated: C 63.54, H 6.59; found: C 63.90, H 6.45.

Preparation of compounds 14 and 15:

[0089] The preparation method is identical to the above described method involving the Tetrakis (triphenylphosphine) palladium (0), the only one difference was the use of dioxane instead of ethanol.

##STR00018##

[0090] .sup.1H NMR (300 MHZ, DMSO): 8.01-7.95 (m, 4H), 7.83-7.77 (m, 4H), 7.16 (s, 2H), 4.17 (t, J=4.6 Hz, 4H), 3.68 (t, J=4.6 Hz, 4H), 3.56-3.45 (m, 48H), 3.22 (s, 6H).

[0091] .sup.13C NMR (126 MHz, DMSO): 167.28, 149.80, 129.54, 129.41, 128.96, 128.75, 115.89, 71.27, 69.92, 69.88, 69.77, 69.57, 68.99, 68.62, 58.04./ As the carbons on alkyl chains are similar to each other depending on resolution number of carbon peak on this region (aliphatic) could be different.

[0092] LRMS (ESI+) for compound 14 calculated: C.sub.50H.sub.74O.sub.20, 995.12; found: C.sub.50H.sub.74O.sub.20K, 1033.44

##STR00019##

[0093] .sup.1H NMR (300 MHZ, DMSO) 8.45 (t, J=1.6 Hz, 2H), 8.39 (d, J=1.6 Hz, 4H), 7.23 (s, 2H), 4.20-4.14 (m, 6H), 3.69-3.63 (m, 12H), 3.45 (d, J=4.9 Hz, 38H), 3.2 (s, 6H).

[0094] LRMS (ESI+) for compound 15 calculated: C.sub.52H.sub.74O.sub.24, 1083.14; found: C.sub.52H.sub.74O.sub.24K, 1121.42

Synthesis and Characterization of the MOFs:

[0095] The preparation of the different MOFs starting from the organic compounds according to formula (II) was performed according to the scheme reported on FIG. 2.

[0096] SUM-103 and SUM-102: In a 10 ml dram vial, 0.018 mmol ligand (compound 5 or 6) are tared and dissolved in a mixture of 4 ml DMF and 1,3 ml water. Then, 0,072 mmol (17,5mg) of Cu(NO.sub.3).sub.2.3H.sub.2O was added to the solution and dissolved in the solution. Finally, 33 l of concentrated HCl was added, the vial is closed and put into dry bath at 80 C. After 24 h, the obtained microcrystalline powder is filtered and washed with DMF to get 14 mg (48% yield) of the MOF SUM-103 and 12.5 mg (45% yield) of the MOF SUM-102.

[0097] SUM-403: In a 10 ml dram vial, 0.009 mmol ligand (compound 6) are tared and dissolved in a 2 ml DMF. Then, 0.054 mmol (13.8 mg) of Mg(NO.sub.3).sub.2x6H.sub.2O was added to the solution and dissolved in the solution. Finally, 2 drops 10 times diluted HCl was added, the vial is closed and put into dry bath at 120 C. After 24 to 48 h, the obtained microcrystalline powder is filtered and washed with.

[0098] FT/IR spectra of MOFs with their corresponding ligands are shown in FIGS. 3 and 4. (H4L (glyme): is for compound 5; H4L (glyme): is for compound 6).

[0099] Since the side chains could not be located by XRD, their presence was established by

[0100] FT-IR analysis (see ESI). Indeed, CH stretching vibrations (2890 cm.sup.1) and the skeletal vibrations of aromatic rings or CCO chains (1200 and 1505 cm.sup.1) demonstrated the presence of backbone and side chains.

[0101] The formation of MOFs can also be deduced from the CO stretching band shifted to low energies due to the coordination of the carboxylate groups to Cu (1630 cm.sup.1). Also, CuO bond elongation band could be observed at 730 cm.sup.1.

Thermal Stability (FIG. 5):

[0102] TGA analysis up to 450 C. under nitrogen of SUM-102 and SUM-103 are characterized by nearly the same pattern. First phase occurs in two waves of solvents evaporation, one below 50 C. for most volatile solvents and a second one between 70 and 200 C. for less volatile ones. Decomposition of MOFs started at 280 C. and 289 C. respectively. Therefore, addition of oxygen rich side chains does not influence the thermal stability of MOF's.

Stability in Water of the Two MOFs: SUM-102 and SUM-103 (FIG. 6);

[0103] The presence of ethylenoxy units confers to the SUM-102, and more particularly to SUM-103 with two ethylenoxy units, an excellent resistance to water. This after treatment for 8 hours at 160 C. and re-exposure to ambient air, whereas in the case of SUM-102 a loss of crystallinity was observed, SUM-103 appeared to be stable.

N.SUB.2 .Adsorption/BET Surface (FIG. 7);

[0104] The nitrogen adsorption of SUM-102 and SUM-103 is displayed on FIG. 7. Despite larger side chains of H4L(diglyme)2 ligand, SUM-103 demonstrates higher surface area. It can therefore be seen that the material with the longest side chains carrying two ethylenoxy units has a greater asorption capacity than the material with only one ethylenoxy unit in the side chains.

[0105] The BET surface area measured for SUM-102 are 869 m.sup.2/g (N.sub.2) versus 846 m.sup.2/g (Ar) and for SUM-103 are 1058 m.sup.2/g (N.sub.2) versus 1016 m.sup.2/g (Ar) and shows type I isotherm characteristic for microporous materials.

CO.sub.2 adsorption

[0106] FIG. 12 shows the CO.sub.2 adsorption by the MOF SUM-103: 38,5 mmol/g adsorbed; 7 mmol/g stays (10 bars, 0 C.).

[0107] FIG. 13 shows the CO.sub.2 adsorption by the MOF SUM-102: 17 mmol/g adsorbed (10 bars, 0 C.).

[0108] FIG. 14 shows the CO.sub.2 adsorption by the MOF SUM-403: 27 mmol/g adsorbed (10 bars, 0 C.).

Dye Adsorption

Methylene Blue Adsorption:

[0109] The adsorption capacity of Methylene Blue was calculated based on Equation (1) [4]-[6]. The equilibrium adsorption capacity of adsorbent was calculated using Equation (2) [6].

[00001]$\begin{array}{cc}\mathrm{Qt}=\left(\mathrm{Co}-\mathrm{Ct}\right).Math.V/m& \left(1\right)\end{array}$$\begin{array}{cc}\mathrm{Qe}=\left(\mathrm{Co}-\mathrm{Ce}\right).Math.V/m& \left(2\right)\end{array}$

where Qt and Ct define the adsorption capacity of the adsorbent (mg/g) and the adsorbate concentration (mg/L), respectively. V represents the volume of adsorbate solution and m the mass of MOF adsorbent. Likewise, Qe and Ce define the adsorption capacity of adsorbent and adsorbate concentration (mg/L), respectively, at the equilibrium conditions.

[0110] The MB isotherms were fitted with Langmuir and Freundlich models in order to calculate the maximal adsorption capacity and get insights about the nature of the adsorption. Linear form of Langmuir equation is expressed as indicated below:

[00002]$\begin{array}{cc}\frac{c_e}{Q_e}=\frac{1}{Q_m{K}_L}+\frac{c_e}{Q_m}& \left(3\right)\end{array}$

[0111] Ce is the equilibrium concentration, Qe is equilibrium uptake capacity. KL and Qm are obtained from the slope and the intercept of Ce/Qe vs Qe plot. R2 of the linear plot is 0.9992 which shows applicability of this model.

[0112] Besides, the separation factor-RL is calculated with Eq (4).

[00003]$\begin{array}{cc}{R}_L=\frac{1}{1+C_m{K}_L}& \left(4\right)\end{array}$

[0113] Cm is maximal initial concentration of methylene blue. The RL shows favorability of adsorption. The value between 0 and 1 shows good adsorption.

[0114] To fit the data to Freundlich model the Eq (5) was used:

[00004]$\begin{array}{cc}\ln Q_e=\ln K_F+\frac{1}{n}\ln C_e& \left(5\right)\end{array}$

[0115] To find KF and 1/n (adsorption constants), the plot of InQe vs InCe were drawn. R2 is 0.7507 which doesn't show a good agreement of this model. The values of adsorption constants for both isotherms are summarized in Table 1.

TABLE-US-00001 TABLE 1 parameters of isotherm modelling for SUM-103 Isotherm model Constants Langmuir Q.sub.m (mg/g) 194 K.sub.L (L/mg) 0.0777 R.sub.L 0.0605 R.sup.2 0.9992 Freundlich K.sub.F (mg/g) 39.1629 1/n 0.3429 R.sup.2 0.7507

[0116] In order to properly describe the adsorption process, two popular methods for studying the adsorption kinetics were applied: Pseudo-first order (PFO) and pseudo second order (PSO). Linear equation of PFO (6) and PSO (7) could be expressed as below:

[00005]$\begin{array}{cc}\ln \left(Q_e-Q_t\right)=\ln Q_e-k_{1}t& \left(6\right)\end{array}$$\begin{array}{cc}\frac{t}{Q_t}=\frac{t}{Q_e}+\frac{1}{k_2{Q}_e^2}& \left(7\right)\end{array}$

[0117] Qe and Qt are the amounts of methylene blue adsorbed (mg/g) on MOFs at equilibrium and at the time t. k.sub.1(min.sup.1) and k.sub.2(g/mg.Math.min) are the rate constants of PFO and PSO, respectively.

TABLE-US-00002 Kinetic model Constants Pseudo First K.sub.1 (L/min) 0.0042 Order Q.sub.e (mg/g) 2.29 R.sup.2 0.9959 Pseudo Second K.sub.2 (g/mg .Math. min) 0.0041 Order Q.sub.e (mg/g) 15.21 R.sup.2 0.9997

[0118] FIG. 8: Crystals of SUM-102 and SUM-103 are observed under Scanning Electron Microscope. Photographs in FIG. 8 show for SUM-103 size around 10-20 m, as also observed for SUM-102.

[0119] Dyes (methylene blue and alizarin yellow R) adsorption capacity of both MOFs have been evaluated. In case of SUM-103, both isothermal adsorption and kinetic studies were performed. The adsorption parameters have been determined in water (neutral pH) at 30 C. (for isotherm). Both SUM-102 and SUM-103 have been compared under identical conditions. The values of dyes adsorption percentage of dye solutions (10 ml; 10 mg/l) over 3 mg MOF after 48 h and at 30 C. are given in table 2.

TABLE-US-00003 TABLE 2 adsorption of dyes versus MOFs sample (by wt % of dyes adsorbed over MOFs) SUM-102 (%) SUM-103 (%) Alizarin Yellow R 64 77 Methylene blue 83 94

[0120] Those values show that methylene blue is more efficiently adsorbed than alizarin yellow R. Also, we observe significant increase in adsorbance with increasing side chains length. The study of the adsorption of methylene blue (MB) on SUM-103 was extended by measurements of isothermal adsorption capacity and a kinetic study, details of these measurements are available in SI. The adsorption protocol was carried out using the batch method by adding 20, 50, 100 and 200 ppm methylene blue solutions over 3 mg MOF in different vials (10 mL) and then placed in the oven at 30 C. After adsorption of methylene blue, the colour of the MOF's changed from blue to deep-blue. Adsorption of methylene blue on MOFs was also assessed by the presence of characteristic strong bands of methylene blue in FT-IR spectrum of final materials (FIG. 9: from left to the right, SUM-103; adsorption kinetics, 2,5 ml, 15 mg/l MB solution after 24 h at room temperature, FT-IR comparison before and after adsorption). After 24 h, the supernatant of methylene blue solution was analysed using a UV-VIS spectrophotometer at 664 nm. FIG. 10 gives Langmuir and Freundlich modelling of MB adsorption of SUM-103. FIG. 11 gives PFO and PSO modelling of MB adsorption of SUM-103 at room temperature.

[0121] The isothermal adsorption capacities were modeled according to the models of Langmuir and Freundlich. It is observed that the quantity of methylene blue which binds to the material is 194 mg/g (Langmuir) for SUM-103.

Preparation of SUM-102, SUM-103, and Others MOFs, Starting From the Organic Compounds Being Selected Among the Compounds According to Formula (I) in Connection with the FIGS. 15 to 19:

[0122] FIG. 15 shows the network of SUM-102 (or Cu@H4L2 or Cu@10). SUM-103 (n=2) and SUM-104 (n=3) have the same PXRD.

[0123] Crystallization conditions: heating of DMF/H.sub.2O solution (4/1.3 mL) of compound 5 (H4L2) (10 mg, 1 eq) and Cu(NO.sub.3).sub.2*3H.sub.2O (17.9 mg, 4.1 eq) and 33 L of HCl (12 M) at 80 C. for 24 h.

[0124] The same topology crystals were obtained with Zn(NO.sub.3).sub.2*6H.sub.2O (4.1 eq) with compound 6 (H4L3) (1 eq) in DMF (2 mL).

[0125] For CO2 adsorption tests slightly modified protocol was used. But obtained MOF is the same.

TABLE-US-00004 TABLE 3 Chemical formula C.sub.14H.sub.15CuO.sub.7 Formula weight 358.80 g/mol Temperature 173(2) K Wavelength 0.71073 Crystal system trigonal Space group R 3 m Unit cell dimensions a = 18.5565(7) = 90 b = 18.5565(7) = 90 c = 38.7407(16) = 120 Volume 11552.9(10) .sup.3 Z 2 Density (calculated) 0.103 g/cm.sup.3 Absorption coefficient 0.097 mm.sup.1 F(000) 368 Theta range for data collection 1.37 to 27.48 Index ranges 23 <= h <= 24, 22 <= k <= 23, 50 <= l <= 50 Reflections collected 36566 Independent reflections 3224 [R(int) = 0.0884] Refinement method Full-matrix least-squares on F.sup.2 Data / restraints / parameters 3224 / 2 / 107 Goodness-of-fit on F.sup.2 0.882 /.sub.max 0.004 Final R indices 2575 data; I > 2(I) R1 = 0.0865, wR2 = 0.2479 all data R1 = 0.1040, wR2 = 0.2680 Largest diff. peak and hole 1.440 and 1.076 e.sup.3

[0126] FIG. 16 shows the network of SUM-403 (or Mg@H4L3).

[0127] Crystallization conditions: heating of DMF solution (2 mL) of compound 6 (H4L3) (3 mg, 1 eq) and Mg(NO.sub.3).sub.2*6H.sub.2O (12 mg, 10 eq) and 2 drops of HCl (3.7%) at 100 C. for 24 h.

TABLE-US-00005 TABLE 4 Chemical formula C.sub.19H.sub.23MgNO.sub.8.50 Formula weight 425.69 g/mol Temperature 173(2) K Wavelength 0.71073 Crystal size 0.120 0.130 0.140 mm Crystal system monoclinic Space group P 1 21 1 Unit cell dimensions a = 10.0803(12) = 90 b = 18.2435(18) = 101.595(5) c = 14.2050(17) = 90 Volume 2559.0(5) .sup.3 Z 4 Density (calculated) 1.105 g/cm.sup.3 Absorption coefficient 0.108 mm.sup.1 F(000) 896 Theta range for data collection 1.46 to 28.13 Index ranges 13 <= h <= 13, 23 <= k <= 21, 18 <= l <= 18 Reflections collected 31265 Independent reflections 11883 [R(int) = 0.1269] Max. and min. transmission 0.9870 and 0.9850 Data / restraints / parameters 11883 / 45 / 659 Goodness-of-fit on F.sup.2 1.279 /.sub.max 4.676 Final R indices 6799 data; I > 2(I) R1 = 0.1119, wR2 = 0.2495 all data R1 = 0.1868, wR2 = 0.2840 Absolute structure parameter 0.2(3) Largest diff. peak and hole 0.781 and 0.585 e.sup.3 R.M.S. deviation from mean 0.135 e.sup.3

[0128] FIGS. 17 shows the Network of SUM-552 (or Zn@H2L2@bipy)

[0129] Crystallization conditions: heating of DMF/DMA solution (1/1 mL) of compound 11 (H2L2) (6 mg, 1 eq) and Zn(NO.sub.3).sub.2*6H.sub.2O (21 mg, 5.5 eq) and 4,4-bipyridine (3.1 mg, 1.5 eq) at 100 C. for 24 h.

TABLE-US-00006 TABLE 5 Chemical formula C.sub.36H.sub.32N.sub.2O.sub.8Zn Formula weight 686.00 g/mol Temperature 173(2) K Wavelength 0.71073 Crystal size 0.150 0.180 0.190 mm Crystal system triclinic Space group P 1 Unit cell dimensions a = 8.6864(4) = 73.801(2) b = 11.4284(5) = 83.284(2) c = 17.5540(8) = 68.094(2) Volume 1552.44(12) .sup.3 Z 2 Density (calculated) 1.468 g/cm.sup.3 Absorption coefficient 0.849 mm.sup.1 F(000) 712 Theta range for data 1.99 to 28.07 collection Index ranges 11 <= h <= 11, 15 <= k <= 15, 23 <= l <= 23 Reflections collected 240457 Independent reflections 7048 [R(int) = 0.0651] Max. and min. 0.7458 and 0.6346 transmission Data / restraints / parameters 7048 / 9 / 455 Goodness-of-fit on F.sup.2 1.035 /.sub.max 0.001 Final R indices 6696 data; I > 2(I) R1 = 0.0370, wR2 = 0.0922 all data R1 = 0.0392, wR2 = 0.0940 Largest diff. peak and hole 1.163 and 1.173 e.sup.3 R.M.S. deviation from 0.67.sup.3 mean

[0130] FIG. 18 shows the network of SUM-503 (or Zn@H2L3):

[0131] Crystallization conditions: heating of DMF/H.sub.2O/CH.sub.3OH solution (1/1/1 mL) of compound 12 (H2L3) (10 mg, 1 eq) and Zn(CH.sub.3COO).sub.2*2H.sub.2O (45 mg, 13.5 eq) at 120 C. for 48 h.

TABLE-US-00007 TABLE 6 Formula C.sub.180H.sub.30N.sub.30O.sub.30Zn Space group P 1 Cell lengths a 18.0412(8) b 20.5164(11) c 28.7012(13) Cell angles 87.969(2) 71.835(2) 64.132(2) Cell volume 9019.56 Z Z: 2 R factor (%) 15.26

[0132] FIG. 19 shows the network of SUM-603 (or Zr@H2L3):

[0133] Crystallization conditions: heating of DMF (2 mL) solution of compound 12 H2L3 (4 mg, 1 eq) and ZrCl.sub.4 (4.7 mg, 3 eq) and benzoic acid (50 mg, 58 eq) at 120 C. for 24 h.

TABLE-US-00008 TABLE 7 Formula C.sub.6O.sub.16Zr.sub.3 Space group F m 3 m Cell lengths a 32.5040(8) b 32.5040(8) c 32.5040(8) Cell angles 90 90 90 Cell volume 34340.8 Z 48 R factor (%) 17.45

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