* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
3.485 g (0.01 mol) of 1,3,5-tris(4-methylphenyl)benzene, 0.0029 g (1 molpercent) of cobaltous nitrate, 0.005482g (1equiv) of ammonium cerium nitrate, 0. 0106g (0.1equiv) of sodium carbonate additive, 0.04mol of 30percent hydrogen peroxide and 5mL of solvent dimethyl succinate and 7.971mg (0.1equiv) The indoleidine ligand was put into a dry and clean pressure-resistant tube, and after heating to 110 °C, the reaction was stopped after the pressure (gauge pressure) was 2.0 MPa for 6 h, the reaction was stopped, and the reaction system was extracted with ethyl acetate. Three times, the obtained product was subjected to removal of the solvent under reduced pressure, and then purified by column chromatography to obtain 1,3,5-tris(4-carboxyphenyl)benzene to give the product 4.2469 g, yield 97percent.
92%
With 2-aminoisonicotinic acid; oxygen; antimony(III) acetate; acetic anhydride; acetic acid; potassium nitrate; 1-aza-adamantane-1-oxide; Dimethyl succinate In 1,2-dichloro-benzene at 180℃; for 12 h;
General procedure: 21) Preparation of Y-type polybiphenyl polycarboxylic acid (Formula (I) to (II)a=1) from polymethylpolybiphenyl,[1,3,5-Tris(4-methylphenyl)benzene\(Acetyl acetate+Antimony acetate+Antimony oxide)\2-aminopyridine-4-carboxylic acid\Potassium nitrate\2-Azaadamantane-N -Oxygen radicals,1.0MPa oxygen(dimethyl succinate + dichlorobenzene + acetic acid)\180°C\12 hours\(1.00.1/0.1/0.1/0.)], operated as in Example 1, with a yield of 92percent. _: (1) Preparation of Y-type polybiphenyl polycarboxylic acid from polymethylpolybiphenyl (formula (I) to (II)a=1),[1,3,5-tris(4-methylphenyl)benzene\(cobalt chloride + acetylacetonate)\2-aminopyridine sodium dodecyl fatty acid (2,2,6,6-tetramethyl piperidine nitrogen oxide (also known as Tempo) + potassium persulfate),1.0MPa Oxygen (dimethyl succinate + acetic acid)\140°C\24 hours\(1.0/0.005/0.005/0.005/0.005)]
90%
at 100℃; for 12 h;
13.85 g (0.01 mol) of 1,3,5-tris(4-methylphenyl)benzene 0.01883 g (1 molpercent) of a Tris derivative modified Fe-Anderson type polyacid ([N(C4H9)4]3 [FeMo6O18{(OCH2)3CNH2}2]),0.0106 g (0.1 equiv) of sodium carbonate additive,30percent by weight of hydrogen peroxide containing 0.03 mol of hydrogen peroxide and 30 mL of solvent dimethyl succinate were put into a dry and clean pressure tube.After heating to 100 ° C,After the reaction was carried out for 12 hours under a pressure (gauge pressure) of 1.0 MPa,Stop the reaction,The reaction system was extracted 3 times with ethyl acetate.The obtained product is removed under reduced pressure,Column chromatography to obtain 1,3,5-tris(4-carboxyphenyl)benzene,Get the product 3.9404g,The yield was 90percent.
Reference：
[1] Patent: CN108218685, 2018, A, . Location in patent: Paragraph 0028; 0030; 0031; 0032
[2] Patent: CN107759460, 2018, A, . Location in patent: Paragraph 0071-0093
[3] Patent: CN108484380, 2018, A, . Location in patent: Paragraph 0031; 0033; 0035; 0037; 0038; 0039
[4] Journal fuer Praktische Chemie (Leipzig), 1890, vol. <2> 41, p. 414[5] Journal fuer Praktische Chemie (Leipzig), 1893, vol. <2> 47, p. 420
[6] Tetrahedron, 1973, vol. 29, p. 2305 - 2313
2
[ 117100-41-1 ]
[ 50446-44-1 ]
Yield
Reaction Conditions
Operation in experiment
92%
With water; sodium hydroxide In tetrahydrofuran; methanol
Compound C (2.0 g, 4.2 mmol) was suspended in 60 mE THF/MeOH (v:v=1:1), and 30 mE 10percent NaOH solution was added. The mixture was stirred overnight. The pH value was adjusted to approximately 2 using hydrochloric acid. The resulting white precipitate was collected by filtration, washed with water, and dried under vacuum to give El 5 (1.7 g, 92percent). ‘H NMR (CDC13): ö=3.97 (s, 9H), 7.90 (d, 2H), 8.06 (d, 2H), 8.44 (d, 2H) 8.49 (t, 1H).
92%
With methanol; sodium hydroxide In tetrahydrofuran
Compound C (2.0 g, 4.2 mmol ) was suspended in 60 mL THF / MeOH (v :v = 1:1), and 30 mL 10percent NaOHsolution was added. The mixture was stirred overnight. The pH value was adjusted to approximately 2 using hydrochloricacid. The resulting white precipitate was collected by filtration, washed with water, and dried under vacuum to give L15(1.7 g, 92percent). 1H NMR (CDCl3): δ = 3.97 (s, 9H), 7.90 (d, 2H), 8.06 (d, 2H), 8.44 (d, 2H) 8.49 (t, 1H).
92%
With water; sodium hydroxide In tetrahydrofuran; methanol
Compound C (2.0 g, 4.2 mmol ) was suspended in 60 mL THF / MeOH (v :v = 1 :i), and 30 mL 10percent NaOH solution was added. The mixture was stirred overnight. The pH value was adjusted to approximately 2 using hydrochloric acid. The resulting white precipitate was collected by filtration, washed with water, and dried under vacuum to give L15 (1.7 g, 92percent). NMR (CDC13): δ = 3.97 (s, 9H), 7.90 (d, 2H), 8.06 (d, 2H), 8.44 (d, 2H) 8.49 (t, iH).
Reference：
[1] Patent: US2015/152123, 2015, A1, . Location in patent: Paragraph 0137; 0140; 0141
[2] Patent: EP2876112, 2015, A1, . Location in patent: Paragraph 0151; 0153
[3] Patent: WO2015/173553, 2015, A1, . Location in patent: Page/Page column 37
[4] Journal of the American Chemical Society, 1959, vol. 81, p. 257,259
[5] Tetrahedron, 2010, vol. 66, # 19, p. 3553 - 3563
[6] Journal of the American Chemical Society, 2015, vol. 137, # 4, p. 1663 - 1672
3
[ 124-38-9 ]
[ 7511-49-1 ]
[ 50446-44-1 ]
Yield
Reaction Conditions
Operation in experiment
0.29 g
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -65 - -60℃; for 1 h; Inert atmosphere Stage #2: With hydrogenchloride In tetrahydrofuran; hexane; water at -65 - -60℃; for 1 h; Inert atmosphere
A mixture of 0.8 kg of 4-bromoacetophenone by Sigma-Aldrich Japan, KK., 40 ml of sulfuric acid and 1.2 kg ofpotassium disulfate was stirred at 180°C for 18 hours. After stirring, 3.0 L of ethanol was added to the mixture, whichwas heated to reflux for 7 hours. It was then allowed to naturally cool to room temperature, producing a precipitate whichwas filtered out. After adding 3.0 L of water to the filtered precipitate and heating to reflux for 1 hour, the reaction mixturewas allowed to naturally cool to room temperature. The reaction mixture was filtered and rinsed with 0.5 L of ethanol.In this manner there was obtained 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene. [0086] A solution comprising 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene and 7.2 L of tetrahydrofuran was cooledto-65°C under an argon gas atmosphere. A 1.6 mol/L butyllithium n-hexane solution (2.1 L) by Wako Pure ChemicalIndustries, Ltd. was then added dropwise at -65°C to -60°C. After reaction at -65°C for 1 hour, CO2 gas was bubbledthrough for 1 hour at -65°C to -60°C. A 2.5 L portion of 1N-hydrochloric acid was added dropwise to the reaction product,and the deposited precipitate was filtered out to obtain 0.40 g of a crude product of the aromatic carboxylic acid representedby formula (5). The crude product was rinsed with tetrahydrofuran and then with hexane and dried under reducedpressure to obtain 0.29 g of the aromatic carboxylic acid represented by formula (5).
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1988, p. 1251 - 1258
[2] Journal of the American Chemical Society, 2004, vol. 126, # 3, p. 884 - 890
[3] RSC Advances, 2013, vol. 3, # 6, p. 1902 - 1915
[4] Patent: EP2586766, 2013, A1, . Location in patent: Paragraph 0085; 0086
4
[ 124-38-9 ]
[ 15797-52-1 ]
[ 50446-44-1 ]
Reference：
[1] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
5
[ 124-38-9 ]
[ 15797-52-1 ]
[ 50446-44-1 ]
Reference：
[1] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
6
[ 109613-00-5 ]
[ 50446-44-1 ]
Reference：
[1] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
[2] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
7
[ 99-93-4 ]
[ 50446-44-1 ]
Reference：
[1] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
[2] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
8
[ 3609-53-8 ]
[ 50446-44-1 ]
Reference：
[1] Journal of the American Chemical Society, 1959, vol. 81, p. 257,259
[2] Journal of the American Chemical Society, 1959, vol. 81, p. 257,259
9
[ 104-15-4 ]
[ 50446-44-1 ]
Reference：
[1] Journal of the American Chemical Society, 1959, vol. 81, p. 257,259
10
[ 214049-70-4 ]
[ 50446-44-1 ]
Reference：
[1] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
[2] European Journal of Organic Chemistry, 1998, # 9, p. 1811 - 1821
With pyridine; ammonium cerium (IV) nitrate; dihydrogen peroxide; sodium carbonate; cobalt(II) nitrate; at 110℃; under 15001.5 Torr; for 6h;Green chemistry;
3.485 g (0.01 mol) of <strong>[50446-43-0]1,3,5-tris(4-methylphenyl)benzene</strong>, 0.0029 g (1 mol%) of cobaltous nitrate, 0.005482g (1equiv) of ammonium cerium nitrate, 0. 0106g (0.1equiv) of sodium carbonate additive, 0.04mol of 30% hydrogen peroxide and 5mL of solvent dimethyl succinate and 7.971mg (0.1equiv) The indoleidine ligand was put into a dry and clean pressure-resistant tube, and after heating to 110 C, the reaction was stopped after the pressure (gauge pressure) was 2.0 MPa for 6 h, the reaction was stopped, and the reaction system was extracted with ethyl acetate. Three times, the obtained product was subjected to removal of the solvent under reduced pressure, and then purified by column chromatography to obtain 1,3,5-tris(4-carboxyphenyl)benzene to give the product 4.2469 g, yield 97%.
92%
With 2-aminoisonicotinic acid; oxygen; antimony(III) acetate; acetic anhydride; acetic acid; potassium nitrate; 1-aza-adamantane-1-oxide; Dimethyl succinate; In 1,2-dichloro-benzene; at 180℃; under 7500.75 Torr; for 12h;
General procedure: 21) Preparation of Y-type polybiphenyl polycarboxylic acid (Formula (I) to (II)a=1) from polymethylpolybiphenyl,[1,3,5-Tris(4-methylphenyl)benzene(Acetyl acetate+Antimony acetate+Antimony oxide)2-aminopyridine-4-carboxylic acidPotassium nitrate2-Azaadamantane-N -Oxygen radicals,1.0MPa oxygen(dimethyl succinate + dichlorobenzene + acetic acid)180C12 hours(1.00.1/0.1/0.1/0.)], operated as in Example 1, with a yield of 92%. _: (1) Preparation of Y-type polybiphenyl polycarboxylic acid from polymethylpolybiphenyl (formula (I) to (II)a=1),[<strong>[50446-43-0]1,3,5-tris(4-methylphenyl)benzene</strong>(cobalt chloride + acetylacetonate)2-aminopyridine sodium dodecyl fatty acid (2,2,6,6-tetramethyl piperidine nitrogen oxide (also known as Tempo) + potassium persulfate),1.0MPa Oxygen (dimethyl succinate + acetic acid)140C24 hours(1.0/0.005/0.005/0.005/0.005)]
90%
With dihydrogen peroxide; sodium carbonate; at 100℃; under 7500.75 Torr; for 12h;
13.85 g (0.01 mol) of <strong>[50446-43-0]1,3,5-tris(4-methylphenyl)benzene</strong> 0.01883 g (1 mol%) of a Tris derivative modified Fe-Anderson type polyacid ([N(C4H9)4]3 [FeMo6O18{(OCH2)3CNH2}2]),0.0106 g (0.1 equiv) of sodium carbonate additive,30% by weight of hydrogen peroxide containing 0.03 mol of hydrogen peroxide and 30 mL of solvent dimethyl succinate were put into a dry and clean pressure tube.After heating to 100 C,After the reaction was carried out for 12 hours under a pressure (gauge pressure) of 1.0 MPa,Stop the reaction,The reaction system was extracted 3 times with ethyl acetate.The obtained product is removed under reduced pressure,Column chromatography to obtain 1,3,5-tris(4-carboxyphenyl)benzene,Get the product 3.9404g,The yield was 90%.
With methanol; sodium hydroxide; In tetrahydrofuran;
Compound C (2.0 g, 4.2 mmol ) was suspended in 60 mL THF / MeOH (v :v = 1:1), and 30 mL 10% NaOHsolution was added. The mixture was stirred overnight. The pH value was adjusted to approximately 2 using hydrochloricacid. The resulting white precipitate was collected by filtration, washed with water, and dried under vacuum to give L15(1.7 g, 92%). 1H NMR (CDCl3): delta = 3.97 (s, 9H), 7.90 (d, 2H), 8.06 (d, 2H), 8.44 (d, 2H) 8.49 (t, 1H).
92%
With water; sodium hydroxide; In tetrahydrofuran; methanol;
Compound C (2.0 g, 4.2 mmol ) was suspended in 60 mL THF / MeOH (v :v = 1 :i), and 30 mL 10% NaOH solution was added. The mixture was stirred overnight. The pH value was adjusted to approximately 2 using hydrochloric acid. The resulting white precipitate was collected by filtration, washed with water, and dried under vacuum to give L15 (1.7 g, 92%). NMR (CDC13): delta = 3.97 (s, 9H), 7.90 (d, 2H), 8.06 (d, 2H), 8.44 (d, 2H) 8.49 (t, iH).
92%
With water; sodium hydroxide; In tetrahydrofuran; methanol;
Compound C (2.0 g, 4.2 mmol) was suspended in 60 mE THF/MeOH (v:v=1:1), and 30 mE 10% NaOH solution was added. The mixture was stirred overnight. The pH value was adjusted to approximately 2 using hydrochloric acid. The resulting white precipitate was collected by filtration, washed with water, and dried under vacuum to give El 5 (1.7 g, 92%). ?H NMR (CDC13): oe=3.97 (s, 9H), 7.90 (d, 2H), 8.06 (d, 2H), 8.44 (d, 2H) 8.49 (t, 1H).
A mixture of 0.8 kg of 4-bromoacetophenone by Sigma-Aldrich Japan, KK., 40 ml of sulfuric acid and 1.2 kg ofpotassium disulfate was stirred at 180C for 18 hours. After stirring, 3.0 L of ethanol was added to the mixture, whichwas heated to reflux for 7 hours. It was then allowed to naturally cool to room temperature, producing a precipitate whichwas filtered out. After adding 3.0 L of water to the filtered precipitate and heating to reflux for 1 hour, the reaction mixturewas allowed to naturally cool to room temperature. The reaction mixture was filtered and rinsed with 0.5 L of ethanol.In this manner there was obtained 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene. [0086] A solution comprising 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene and 7.2 L of tetrahydrofuran was cooledto-65C under an argon gas atmosphere. A 1.6 mol/L butyllithium n-hexane solution (2.1 L) by Wako Pure ChemicalIndustries, Ltd. was then added dropwise at -65C to -60C. After reaction at -65C for 1 hour, CO2 gas was bubbledthrough for 1 hour at -65C to -60C. A 2.5 L portion of 1N-hydrochloric acid was added dropwise to the reaction product,and the deposited precipitate was filtered out to obtain 0.40 g of a crude product of the aromatic carboxylic acid representedby formula (5). The crude product was rinsed with tetrahydrofuran and then with hexane and dried under reducedpressure to obtain 0.29 g of the aromatic carboxylic acid represented by formula (5).
A 750 mL N,N-dimethylformamide solution of 4,4?,4?-benzene-1,3,5-triyl-tri benzoic acid (H3BTB) (3.0 g, 6.8 mmol) and zinc nitrate hexahydrate (18.0 g, 60.5 mmol) was prepared and distributed in 30 equal portions to capped 60 mL glass jars. The vessels were then heated for 16 hr in a 100 C. oven, after which the pale yellow needles of MOF-178 were harvested by filtration and rinsed with N,N-dimethylformamide followed by chloroform. Immersion of the product in chloroform (60 mL) for greater than 3 days, followed by evacuation for 12 hr (25 deg. C., <1 mTorr) yields the activated material Zn4O(BTB)2 (FW 1154 g/mol, yield 3.2 g, 81%). Similar results were observed when other glass vessels were used. Anhydrous acetonitrile can also be used as the exchange guest, with little effect on the surface area of the final product.
With zinc(II) nitrate; at 20 - 100℃; for 30.3333h;
A N,N-diethylformamide (DEF) solution containing 4,4?,4?-benzene-1,3,5-triyl-tri benzoic acid (H3BTB; 0.005 g, 1.14?10?5 mol) and zinc nitrate hexahydrate Zn(NO3)2.6H2O (0.020 g, 6.72?10?5 mol) was placed in a Pyrex tube (10 mm?8 mm o.d. x i.d., 150 mm length). The sealed tube was heated at a rate of 2.0 C./min to 100 C., held at 100 C. for 23 hr, and cooled at a rate of 0.2 C./min to room temperature. Block-shaped yellow crystals of MOF-177 were formed and isolated by washing with DEF (4?2 ml) and drying briefly in the air (ca. 1 min) (0.005 g, 32% based on ligand). Anal. Calcd. for C129H201N15O31Zn4=Zn4O(BTB)2.(15DEF)(3H2O): C, 56.96; H, 7.46; N, 7.73. Found: C, 56.90; H, 7.54; N, 7.67. FT-IR (KBr, 4000?400 cm?1): 1643(s), 1607(s), 1591(s), 1546(m), 1406(vs), 1300(w), 1263(w), 1213(w), 1180(w), 1105(w), 1017(w), 857(w), 809(w), 980(s), 708(w), 669(w).
A 3:2 molar ratio of Fe2(SO4)3.x(H2O) (0.06 g, 0.15 mmol) and 1,3,5-tris(4-carboxyphenyl)benzene (H3BTB) (0.044 g, 0.10 mmol) were suspended in a 20 mL solution of a 1:1 ratio of N,N-dimethylformamide (DMF) and pyridine using a 50 mL round bottom flask. 150 muL of neat triethylamine were added to this mixture and the reaction capped and stirred at room temperature for 72 h. A 3 mL aliquot of the stirring heterogeneous reaction solution was placed in a Pyrex tube (i.d.×o.d.=8×10 mm2, 140 mm length). The tube was flash frozen, evacuated, flame sealed and heated to 115 C. (5 C./min) for 42 h and cooled (0.5 C./min) back to room temperature. The octahedral orange crystals of MOP-54 which formed during the isotherm were separated from the amorphous material and yellow crystalline impurity by density separation (bromoform/pyridine). The isolated product (20.2% yield based on H3BTB) was washed with 3×5 mL pyridine and 1×5 mL cyclohexane. Anal. Calcd. for C230H308N34O103Fe12=[NH2(CH3)2]8[Fe12O4(BTB)4(SO4)12(py)12].(DMF)12(py)2(H2O)15: C, 44.19; H, 4.97; N, 7.63. Found: C, 44.15; H, 5.06; N, 7.63. FT-IR (KBr, 3500-400 cm-1): 3425 (vs), 2841 (s), 2809 (m), 2683 (m) 2490 (w), 1715 (m), 1661 (vs), 1611 (s), 1550 (m), 1535 (m), 1413 (vs), 1214 (s), 1125 (vs), 1067 (s), 1036 (s), 991 (s), 857 (m), 810 (m), 785 (s), 701 (m), 665 (m), 607 (s), 505 (s), 417 (m).
In a screw tube there were placed terbium nitrate hexahydrate by Mitsuwa Chemicals Co., Ltd. (565.8 mg, 1.25mmol), 2,4,6-tris-(4-carboxyphenyl)phenol (546.7 mg, 1.25 mmol) and purified water (12.5 mL). A 2M water-solublesodium hydroxide solution (1.0 mL) was then added to the screw tube and the mixture was stirred for 2 minutes. Next,12.5 mL of cyclohexanol was added to the screw tube as a heated liquid, and stirring was continued for 10 minutes.Next, TEFLONR packing was inserted in the screw tube and the cover closed, and the screw tube was placed in anautoclave by Taiatsu Techno and subjected to hydrothermal synthesis at 100C for 48 hours. On the following day, thecontents of the screw tube were filtered, the obtained solid was rinsed with water (10 mL x 2.5 mL x 1), twice with ethanol(10 mL) and twice with acetone (10 mL) and vacuum dried, to obtain a white product. (Yield: 491.8 mg)
After repeating the procedure described above several times, 1.0 g of the obtained aromatic carboxylic acidrepresented by formula (5), 0.86 g of aluminum nitrate nonahydrate by Kishida Chemical Co., Ltd., and N,N-diethylformamideby Tokyo Kasei Kogyo Co., Ltd. (50 mL) were placed in a carbon resin-coated polytetrafluoroethylene crucibleproduced by San-Ai Science Co., Ltd. The crucible was sealed with a stainless steel jacket, and the stainless steel jacketwas dipped for 24 hours in an oil bath prepared to a temperature of 150C. The crucible was then cooled to roomtemperature, and the white precipitate produced in the reaction mixture was filtered out to obtain 1.4 g of a porouscoordination polymer. Identification was carried out in the same manner as Examples 1 and 2.
[Zn(1,3,5-benzenetrisbenzoate)(Hbib)]*2H2O*CH3OH}n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
33%
at 150℃; for 72h;pH 6.0;
A mixture of Zn(OAC)22H2O (0.0443g), H3btb (0.0433g), bib(0.0217g), deionised water (10mL) and CH3OH (5mL) was stirred for 30min in air. The pH of the resulting solution was adjusted to 6 and kept at 150C for 72h. The solution was then cooled to room temperature at rate of 5Ch-1, colorless crystalline product 1 was produced within 33% yield based on Zn. Calcd: C, 60.95; H, 5.37; N: 7.11; found C, 60.66; H, 5.32; N: 7.04. IR (KBr, cm-1): 3441(vs); 3012(m); 1638(vs); 1422(vs); 748(vs); 522(m). Crystal data for 1: C40H42N4O9Zn, Mr=788.15, monoclinic, space group P21/c, a=9.4143(3) A, b=27.4271(9) A, c=17.5489(5) A, beta=119.429(2), V=3946.6(2) A3, Z=4, Dcalcd.=1.326g/cm3, R1[2sigma(I)]=0.0874, wR2(for all data)=0.2315. The compound 1 was weakly diffractors giving poor data and that we were unable to obtain better crystals despite attempt to do so, assuming that was the case. The water and methanol molecules are omitted from the refinement, but are included in the formula. The hole in the final difference Fourier map is at 1.59A from Zn1, and is a consequence of the application of the SQUEEZE procedure. CCDC: 990850.
With triethylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate; In N,N-dimethyl-formamide; at 20℃; for 24h;Inert atmosphere;
General procedure: Under argon atmosphere, the amine (1.0 equiv), the corresponding carboxylic acid (1.0 equiv) and HATU (1.0 equiv) were dissolved in DMF (8 mL/mmol). After addition of Et3N (4.5 equiv), the reaction mixture was stirred at rt during the indicated time. After removing the solvents in vacuo, the crude product was purified by flash column chromatography.
In N,N-dimethyl-formamide; at 150℃; for 72h;High pressure; Autoclave;
General procedure: Solvothermal reaction of H3BTB (0.1 mmol) and Ln(NO3)36H2O(0.1 mmol; Ln = Eu (1), Dy (2)) was performed in a mixture solvents of DMF (5 mL) and H2O (2 mL) in a 15 mL Teflon-lined stainless steel autoclave, which was heated at 150 C for 3 days and then cooled to room temperature at 1.5 C/h. Colourless needle shaped crystals were filtered out and washed with DMF and H2O three times. [Eu(BTB)(H2O)]n (1). Yield based on Eu: 44%. Anal. Calc.for 1: C27H17O7Eu: C, 53.57; H, 2.83. Found: C, 53.45; H, 2.65.
[Zr6O4(OH)4](HCOO)4(H2O)2(OH)2(1,3,5-tris(4-carboxyphenyl)benzene)2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In 20 mL vial, zirconium dichloride oxide octahydrate (12 mg, 0.037 mmol) and l,3,5-tris(4- carboxyphenyl)benzene (H3BTB, 10 mg, 0.023 mmol) were added to N,N- dimethylformamide (DMF, 4 mL). The solution was sonicated for ten minutes. Following the sonication, formic acid (2.5 mL) was added to the solution. The solution was heated at 130 C in preheated oven for five days. The single crystals were collected and washed with DMF (5 x 10 mL) over three hour period. The DMF solvent was then replaced with methanol (9 x 20 mL) over three days period. The methanol was then removed in vacuo (30 mTorr) for 48 hrs.
[Hf6O4(OH)4](HCOO)4(H2O)2(OH)2(1,3,5-tris(4-carboxyphenyl)benzene)2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In (0378) 20 mL vial, hafnium dichloride (12 mg, 0.037 mmol) and l,3,5-tris(4- carboxyphenyl)benzene (H3BTB, 10 mg, 0.023 mmol) were added to N,N- dimethylformamide (DMF, 4 mL). The solution was sonicated for ten minutes. Following the sonication, formic acid (2.5ml) was added to the solution. The solution was heated at 130 C in preheated oven for five days. The single crystals were collected and washed with DMF (5 x 10 mL) over three hour period. The DMF solvent was then replaced with methanol (9 x 20 mL) over three days period. The methanol was then removed in vacuo (30 mTorr) for 48 hrs.
A mixture of Zn(OAc)2 (0.1 mmol), 1,3,5-benzenetribenzoic acid (H3Btb) (0.1 mmol), DMF (8 mL) and HNO3 (0.1 mL) was placed in a vial, heated to 105C for 3 days under autogenous pressure, and then cooled to room temperature at a rate of 5C/h. Colorless crystals were obtained after 4 days. The resulting crystals formed were filtered off, washed with water and dried in air. The yeild was 35% based on Zn.
A1(NO3)-9H2O (90 mg; 0.240 mmol) and H3BTB (75 mg; 0.171 mmol) were added to a 20 mL vial. DMF (14 mL) was added to the vial, and the vial was then sonicated for 10 min at ambient temperature. Formic acid (1.4 mL) was then added to the solution. The solution was placed in a preheated 130 C oven for 48 hours. The resulting single crystals of MOF-521 were obtained from the wall of the vial.
(NH2Me2)2[Mg6O3(4,4′,4″-benzene-1,3,5-triyl-tribenzoate)8/3(H2O)4]*15(dimethyl sulfoxide)*5H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In N,N-dimethyl-formamide; at 120℃; for 48h;
General procedure: Complex 1 was prepared by heating Mg(NO3)2·6H2O and H3BTB in DMF/H2O (5:0.7v/v) at 120C for 48h. It appeared in the form of light yellow cube-shaped crystals and was insoluble in common organic solvents such as DMF, ethanol, chloroform, acetone, 1,4-dioxane, and diethyl ether. Complex 2 was synthesized in the solvent of DMSO/DMF/H2O (5:1.5:1v/v). The remaining reaction conditions for generating 2 are the same as those for 1. 2 also emerged as light yellow cube-shaped crystals and showed similar insolubility to 1. Their structures were determined by single-crystal X-ray diffraction.
[Zn(HBTB)(2-(4,6-di(pyridine-2-yl)pyridine-2-yl)pyridine)]·H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
33%
at 180℃; for 72.5h;pH 6.0;High pressure;
A mixture of Zn(NO3)2·6H2O (0.074 g), H3BTB (0.044 g), pdp (0.031 g), deionisedwater (10 mL) was stirred for 30min in air. The pH of the resulting solution was adjustedto 6 and kept at 180 C for 72 h. The solution was then cooled to room temperatureat rate of 2 C h-1, colorless crystalline product 1 was produced within 33%yield based on Zn. Calcd: C, 67.86; H, 3.95; N: 6.82; Found C, 68.00; H,3.89; N: 6.75.IR (KBr, cm-1): 3441(vs); 3012(m); 1638(vs); 1422(vs); 748(vs); 522(m). Crystaldata for 1: C47H32N4O7Zn, triclinic, space group P-1, a=10.643(5) A, b=13.121(6)A, c=15.291(7) A, alpha=87.996(8), beta=70.237(8), gamma=86.860(9), V=2006.2(16)A3, Z = 2, Dcalcd. = 1.373 g/cm3, R1[2sigma(I)] = 0.0755, wR2(for all data) = 0.2110.CCDC: 1444817.
0.928C27H15O6(3-)*0.072C7H5O2(1-)*Al(3+)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
In N,N-dimethyl-formamide; at 149.84℃; for 24h;Inert atmosphere;
Under a nitrogen atmosphere, aluminum nitrate nonahydrate 1.84 g (4.9 mmol), 1,3,5-tris (4-carboxyphenyl) benzene 2.15 g (4.9 mmol) and benzoic acid 0 . 598 g (4.9 mmol) was dissolved in 107 mL of N, N-diethylformamide, and the mixture was stirred at 423 K for 24 hours.The precipitated metal complex was collected by suction filtration and then washed three times with ethanol.Subsequently, it was dried at 373 K and 50 Pa for 8 hours to obtain 1.57 g of the desired metal complex.The powder X-ray diffraction pattern of the obtained metal complex5shown.[0062]The resulting metal complex 10mg dissolved in 4 wt% sodium hydroxide -d heavy water solution 800mg,1 was subjected to H-NMR measurement.The resulting spectrumFigure 6shows in.As a result of analyzing the spectrum, the integral of the peak of 7.736 ppm (d, 6 H) attributed to the protons at the 3 and 5 positions of the 4-carboxyphenyl group of 1,3,5-tris (4-carboxyphenyl) benzene When the value was set to 1,000, the integrated value of the peak at 7.903 ppm (d, 2 H) attributed to the protons at the 2- and 6-positions of benzoic acid was 25.7, so that the metal complex It was found that the molar ratio of 1,3,5-tris (4-carboxyphenyl) benzene to benzoic acid contained was 1,3,5-tris (4-carboxyphenyl) benzene: benzoic acid = 13: 1 It was.[0063]1from the result of the H-NMR measurement and elemental analysis, the composition formula of the resulting metal complex[Al(C 27H15O . 6)1-x(C. 6 H 5 of 5 COO)x]n(x = 0. 072), respectively."N" means an arbitrary natural number.Theoretical yield[Al(C 27H15 O 6 )0.928(C 6H5 COO) 0.072]N(aluminum: 1,3,5-tris (4-carboxyphenyl) benzene: benzoic acid = 1 : 0.928: 0.072).As a result, the yield of the obtained metal complex was 73%.
0.35 g (0.3 mmol) of Cucumber ring (Q [6]), 0.2 g (1.2 mmol) of CsCl, 0.5 g of H3BTB0.044 g (0.1 mmol).The Q [6] and CsCl were placed in a 250 mL beaker containing 90 mL of distilled water, shaken for 10 min. To disperse the Q [6] particles uniformly, heated to 50 C and stirred with a magnetic stirrer to give a white turbid solution. The H3BTB was then placed in a 50 mL beaker containing 10 mL of distilled water, stirred with a magnetic stirrer, and poured into 1 mL of concentrated aqueous ammonia. After stirring for 10 min, it was poured into the cloudy solution of Q [6] and stirring was continued for 5 h.The stirred solution was then transferred to a high pressure autoclave,The program temperature to 180 C, constant temperature 20h,And then cooled to 50 C,Constant temperature 10h;Close the program temperature oven,The autoclave was cooled to room temperature,After standing for 24h,(BTB3 - Q [6] -Cs +), the structural formula is {Cs6 (H20) 6 (0 [6]), which is an aromatic organic multidentate ligand - cucurbit - ring porous framework polymer. ) 3.2 (8 8) 1112 O} in a yield of 50-60%.
0.4 g (0.3 mmol) of cucumber ring (Q [7]), 0.40 g (2.4 mmol) of CsCl, H3BTB0.044 g (0.1 mmol). Place Q [7] and CsCl in a 250 mL beaker containing 90 mL of distilled water, heat to 60 C, addThe magnet was stirred for 1 h to give a clear solution. Then H3BTB containing 10mL distilled water in a 50mL beaker, by adding magnetic stirring,With stirring, lmL of concentrated aqueous ammonia was injected. After stirring for 10 min, it was poured into a clear solution of Q [7] and stirred for 2 h. Of courseAnd then the temperature of the mixed solution was transferred to a high-pressure reaction kettle. The temperature of the mixture was raised to 180 C and kept at a constant temperature of 20 hours. Then, the temperature was lowered to 50 C and the temperature was kept constant for 10 hours. The oven was closed and the autoclave was cooled to room temperature. After 24h, a colorless block was obtained(BTB3 ~ Q [7] -NH4 +) with the structural formula of {(NuEta4) 6 (0) 6 (6), which is a multi-dimensional porous cucumber ring-based organic framework polymer(Q [7]) 3'2 (BTB) 'xH20} in a yield of 30-40%.
InEu(BTB)<SUB>2.33</SUB>(H<SUB>2</SUB>O)<SUB>2</SUB>(DEF)<SUB>6</SUB>[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With oxalic acid; In methanol; at 105℃; for 72h;
The reaction mixture containing In(NO3)3.5H2O (0.043 mmol, 17 mg), EuCl3.6H2O (0.043 mmol, 16 mg), 1,3,5-Tris(4-carboxyphenyl)benzene (BTB) (0.043 mmol, 19 mg), oxalic acid (OA) (0.065 mmol, 5.85 mg), N,N?-diethylformamide (DEF) (2.5 mL), and MeOH (2.5 mL) was placed in a 20 mL scintillation vial and was heated to 105 C. for 3 days at a rate of 1.5 C./min and cooled to room temperature at a cooling rate of 1 C./min. Crystalline material with rhombic dodecahedron morphology was obtained.
With tetrafluoroboric acid; at 100℃; for 72h;Autoclave;
H3BTB (0.015 mmol, 0.0066 g) and Cd(NO3)2·4H2O (0.03 mmol,0.011 g) were dissolved in N,N?-dimethylacetamide (DMA, 4.0 mL)with a drop of HBF4 (40%) in a 10 mL sealed Teflon-lined autoclave,which was placed in a 100 C oven for 3 days to yield colorlessdiamond-shaped crystals of 1alpha. Yield: 64% based on H3BTB ligand.CHN element analysis: Calcd. (%) for C78H84N6O18Cd3 (Mr =1730.71): C, 54.13; H, 4.89; N, 4.86. Found: C, 54.27; H, 4.52; N,4.66. IR (KBr, cm-1): 3432 (br), 3051 (w), 2936(w), 1671 (vs), 1625(s), 1591(s), 1470(vs), 1374 (w), 1340(w), 1262(m), 1214(w),1099(m), 933 (m), 865(s), 827(m), 787(m), 708(m).
With tetrafluoroboric acid; In methanol; at 20 - 100℃; for 120h;Autoclave;
A mixture of Cd(NO3)2·4H2O (0.03 mmol, 0.011 g), H3BTB(0.015 mmol, 0.0066 g), in 4 mL DMA and 2 mL CH3OH with a dropof HBF4 (40%) was stirred for 30 min at room temperature and thenheated in a 10 mL Teflon-lined autoclave at 100 C for 5 days, yieldingcolorless rhomboid-shaped crystals (1beta). Yield: 53% based on H3BTBligand. CHN element analysis: Calcd. (%) for C78H84N6O18Cd3 (Mr =1730.78): C, 54.13; H, 4.89; N, 4.86. Found: C, 54.45; H, 4.77; N, 4.60.IR (KBr, cm-1): 3433(br), 2930(w), 1678(vs), 1628(s), 1594(s),1473(vs), 1341(w), 1267(m), 1186(w), 1099(s), 1049(w), 937(s),871(vs), 787(m), 750(m), 678(m).
With tetrafluoroboric acid; In methanol; at 20 - 100℃; for 72h;Autoclave;
A mixture of Cd(NO3)2·4H2O (0.03 mmol, 0.011 g), and H3BTB(0.015 mmol, 0.0066 g) in N,N?-dimethylformamide (DMF, 3 mL) andCH3OH (1 mL) with a drop of HBF4 (40%) was stirred for 30 min andthen heated in a 10 mL Teflon-lined autoclave at 100 C for 3 days.After cooling to room temperature slowly, colorless block crystals of 1gammawere collected. Yield: 71% based on H3BTB ligand. CHN elementanalysis: Calcd. (%) for C72H72N6O18Cd3 (Mr = 1646.62): C, 52.52; H,4.41; N 5.10. Found: C, 52.45; H, 3.97; N, 5.43. IR (KBr, cm-1):3443(br), 3063(w), 2936(w), 1678(vs), 1628(s), 1594(s), 1472(vs),
Single-crystal for X-ray structure determinations of compound 2was obtained by slow vapor-diffusion method. A mixture of Cd(NO3)2·4H2O (0.03 mmol, 0.011 g), and H3BTB (0.015 mmol, 0.0066 g), witha drop of HCOOH, were dissolved in 6.0 mL of DMF at roomtemperature, and transferred into a 20 mL test tube. Then a small vialcontaining isopropylamine (0.1 mL) and DMF (2.0 mL) was put in thetest tube above. The test tube was left at 60 C for about two weeks togive colorless prism-shaped crystals of 2. Yield: 22% based on H3BTBligand. CHN element analysis: Calcd. (%) for C37H37N3O11Cd2 (Mr =924.53): C, 48.07; H, 4.03; N 4.55. Found: C, 48.45; H, 3.77; N, 4.30.IR (KBr, cm-1): 3433(br), 3063(w), 2924(w), 1688(vs), 1614(s),1568(s), 1428(vs), 1285(w), 1213(w), 1177(w), 1136(m), 1092(w),1042(m), 892(s), 848(m), 814(s), 740(m), 703(s).The compound could also be obtained by the following procedure: Amixture of Cd(NO3)2·4H2O (0.03 mmol, 0.011 g), H3BTB (0.015 mmol,0.0066 g) with a drop of HCOOH in DMF (8.0 mL) was stirred at roomtemperature for 30 min, and then was subjected to the hydrothermalreaction at 60 C for 5 days. Polycrystalline precipitate was isolatedwith yield about 53% based on H3BTB. The phase purity of the bulkproduct was confirmed by PXRD experiments.
In water; N,N-dimethyl-formamide; at 150℃; for 72h;High pressure; Autoclave;
A mixture of CoCl2·6H2O (0.12 g, 0.5 mmol), H3BTB (0.14 g, 0.33 mmol), bibp (0.14 g, 0.5 mmol),DMF (3 mL) and water (3 mL) was placed in a 25-mL Teon-lined stainless steel vessel andthe mixture was heated at 150 C for 3 days, and then the reaction system was cooled to room temperature. Purple block crystals were obtained in 38% yield (based on Co). Elementalanalysis (%): Calcd.: C, 66.77; H, 3.94; N, 8.65. Found: C, 66.63; H, 3.99; N, 8.68.
3Co(2+)*2C18H14N4*2C27H15O6(3-)*4H2O*2C3H7NO[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
48%
at 150℃; for 72h;High pressure; Autoclave;
General procedure: A mixture of CoCl2·6H2O (0.12 g, 0.5 mmol), H3BTB (0.14 g, 0.33 mmol), bibp (0.14 g, 0.5 mmol),DMF (3 mL) and water (3 mL) was placed in a 25-mL Teon-lined stainless steel vessel andthe mixture was heated at 150 C for 3 days, and then the reaction system was cooled to room temperature.
Complex 1 was synthesized by hydrothermal method in a25 mL Teflon-lined autoclave by heating a mixture of 50-(4-Carboxyphenyl)-[1,10:30,100-terphenyl]-4,400-dicarboxylic acid(0.1 mmol, 0.0439 g), Ho(NO3)2¢6H2O (0.1 mmol, 0.0458 g)and deionized (10 mL) water at 443 K for 5 days under autogenous pressure and then cooled to room temperature slowly.Colourless block-like crystals of 1 were collected by filtrationand washed with distilled water in 79% yield (based on Ho).Anal. Calcd. (%) for C27 H17 N2 O7 Ho : C, 67.36; H, 3.53; N,5.82. Found (%): C, 67.35; H, 3.54; N, 5.85. IR data(KBr, cm1): 1612(w), 1554(s), 1487(w), 1431(s), 1392(vs),1332(m), 1227(w), 1166(m), 1092(w), 1008(w), 956(m), 893(m), 845(w), 775(w), 764(m), 723(m), 668(m).
In N,N-dimethyl-formamide; at 130℃; for 72h;Autoclave; High pressure;
A mixture of H3BTB (0.1 mmol, 43.8 mg), 1,10-phen(0.1 mmol, 18.0 mg) and Eu(NO3)3·6H2O (0.1 mmol,44.6 mg) in H2O (3 mL) and dimethyl formamide (DMF,1 mL) were sealed in a 15 mL Teflon-lined tainless steelautoclave. The autoclave was heated at 130 C flor 3 d underautogenous pressure and then cooled to room temperature ata rate of 2 C/h under ambient conditions. The light yellowcrystals were obtained and washed with H2O. Yield: 76%,based on Eu(NO3)3·6H2O. Elemental analysis (%) Calcd. forcompound 1: C 58.24, H 3.36, N 3.48. Found: C 58.13, H3.54, N 3.28.
bis(4-(2′-methylimidazolyl)phenyl)sulfone[ No CAS ]
[ 50446-44-1 ]
[ 68-12-2 ]
[Cd3(4,4',4''-benzene-1,3,5-triyl-tribenzoate)2(bis(4-(2'-methylimidazol-ylphenyl))sulfone)2]*5DMF[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
In water; at 80℃; for 48h;High pressure;
A mixture of Cd(NO3)2·4H2O (0.0308g, 0.1mmol), H3btb (0.0438g, 0.1mmol), bmis (0.0378g, 0.1mmol), DMF (8ml) and H2O (2ml) was placed in a Teflon reactor (20ml) and heated at 80C for 2days. After gradually cooled to room temperature at a rate of 10C·h-1, colorless crystals of 3 were obtained with 60% yield based on bmis. Anal. Calcd for C109H101N13O21S2Cd3: C, 56.18; H, 4.37; N, 7.81. Found: C, 56.25; H, 4.22; N, 7.70. IR (KBr, cm-1): 3138 (w), 3067 (w), 2362 (w), 1669 (m), 1592 (m), 1540 (m), 1501 (m), 1392 (m), 1301 (m), 1159 (m), 1101 (m), 1016 (w), 854 (w), 809 (w), 784 (m), 770 (w), 667 (w), 621 (m), 583 (w), 472 (w).
With sodium hydroxide; In water; at 120℃; for 96h;Autoclave; High pressure;
General procedure: A mixture of Cd(NO3)2 ·2H2O (0.068 g), H4btec (0.038 g), L(0.035 g), H2O (10 mL) and NaOH (0.016 g) was stirred for 30 min in air, then the suspension was transferred and sealed in a Teflon lined autoclave, which was heated at 120 C and kept for 4 days, then cooled to room temperature leading to the formation of colorless block crystals for compound 1 in 46% yield based on Cd, and manually pick suitable crystal from the precipitation.
6C24H8O24S8(8-)*8C27H15O6(3-)*24Co(2+)*6HO(1-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Ca. 95%
In methanol; at 85℃; for 12h;
Na4H4V (14.5 mg, 0.014 mmol) and H3L (14.5 mg, 0.033 mmol) and CoCl2 (13.3 mg,0.103 mmol) were suspended in 2 mL MeOH. The mixture was heated up at 85 oC in anoven for 12 h. After cooling down to ambient temperature, big purple crystals werecollected and washed by methanol. Yield of PCC-2 is about 95% (according to H4V1).Elemental analysis: calculated (%) for Na30(Et3NH)6 [C360H222S48O198Co24]· 5 MeOH · 10H2O, C 39.56, H 2.96, N 0.69, S 12.64; found (%):C 39.28, H 2.92, N 0.70 S 12.86.ESI-MS: 510.73 (232-), 528.15 (22-), 539.09 (22-), 550.12 (21-), 574.11 (21-), 585.09(20-), 609.99 (19-), 619.98 (19-), 631.94 (19-), 646.49 (18-), 660.50 (18-), 702.87 (17-),748.47 (16-), 760.56 (15-), 772.88 (15-), 881.69 (14-), 971.50 (12-), 979.02 (12-), 990.11(12-), 1102.56 (11-), 1131.84 (11-).
H3[Mn3O3(1,3,5-tris(4-carboxylatophenyl)benzene)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
53%
With 1H-imidazole; In N,N-dimethyl-formamide; at 110℃; for 72h;High pressure;
2.2 Synthesis of Mn-BTB A solution of H3BTB (0.020?g, 0.045?mmol), Mn(OAc)2 (0.010?g, 0.60?mmol), imidazole (0.010?g, 0.60?mmol) and L-BCIP (0.060?g, 0.20?mmol) in 3?mL DMF was sealed in a 23?mL Teflon-lined stainless-steel container, kept at 110?C for 3 days and then cooled to room temperature. The obtained crystals were washed with DMF and H2O and then dried at room temperature in air (yield: 15.6?mg, 53% based on H3BTB). EA and ICP calc'd (%) for C27H18Mn3O9: C 49.80, H 2.79, Mn 25.31; Found: C 49.92, H 2.76, Mn 25.38 for Mn-BTB.
catena-[triaquatris(1,4-dioxane)tetrakis{4,4',4"-benzene-1,3,5-triyltris(benzoate)}hexacopper(II)] 1,4-dioxane tetrasolvate decahydrate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
94%
With (S)-Malic acid; at 100℃;
Compound 3 was synthesized by the reaction of copper(II) nitrate (0.024 g, 0.10 mmol) with 4,4',4"-benzene-1,3,5-triyltris(benzoic acid) (0.018 g, 0.04 mmol) in the presence of S-malic acid (0.016 g, 0.12 mmol) in a 4 : 1dioxane-water mixture (2.0 mL). The reaction was performed in a sealed glass tube on heating to 100 C overnight. The heating was accompanied by the precipitation of dark blue crystals, which were washed with dioxane and dried in air.
catena-[tetraaquamethanoldi-S-malatemonohydro{4,4',4"-benzene-1,3,5-triyltris(benzoate)}tetracopper(II)] tetrahydrate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
at 100℃;
General procedure: Compound 1 was synthesized by the reaction of copper(II) acetate (0.048 g, 0.24 mmol), S-malic acid (S-H3mal) (0.016 g,0.12 mmol), and 4,4,4?-benzene-1,3,5-triyltris(benzoic acid) (H3btb) (0.032 g, 0.072 mmol) in a 1 : 1 methanol-water mixture (2.0 mL). The reaction was performed in a sealed glass tube on heating to 100 C overnight. The heating was accompanied by the formation of blue plate-like crystals and a white amorphous precipitate. The amorphous precipitate was separated by decantation. The crystals were washed with methanol and dried in air. Compound 2 was prepared under conditions similar to those used in the synthesis of compound 1, but starting from R-malic acid instead of S-malic acid.
catena-[tetraaquamethanoldi-R-malatemonohydro{4,4',4"-benzene-1,3,5-triyltris(benzoate)}tetracopper(II)] tetrahydrate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
at 100℃;
General procedure: Compound 1 was synthesized by the reaction of copper(II) acetate (0.048 g, 0.24 mmol), S-malic acid (S-H3mal) (0.016 g,0.12 mmol), and 4,4,4?-benzene-1,3,5-triyltris(benzoic acid) (H3btb) (0.032 g, 0.072 mmol) in a 1 : 1 methanol-water mixture (2.0 mL). The reaction was performed in a sealed glass tube on heating to 100 C overnight. The heating was accompanied by the formation of blue plate-like crystals and a white amorphous precipitate. The amorphous precipitate was separated by decantation. The crystals were washed with methanol and dried in air. Compound 2 was prepared under conditions similar to those used in the synthesis of compound 1, but starting from R-malic acid instead of S-malic acid.
2C27H15O6(3-)*2C12H12N2*C5H5N*3.5Co(2+)*HO(1-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
In N,N-dimethyl-formamide; at 120℃; for 72h;pH 4.9;Autoclave; High pressure;
CoCl2 (0.25 mmol), 1,3,5-Tris(4-carboxyphenyl)benzene (BTB) (0.05 mmol) and 1,2-bis (4-pyridyl) ethane (0.10 mmol) were dissolved in 10 mL of solvent mixture (6 mL milli-Q water + 4 mL DMF) and its pH was 4.9. This solution was sonicated for 5 min and then transferred into a Parr Teflon-lined vessel (23 mL). The vessel was sealed in an autoclave and heated at 120C for 3 days in a programmable oven. Purple coloured needle-shaped crystals of compound 1 were formed. Crystals were washed with milli-Q water and dried under vacuum for further use. The yield of compound 1 is 60% (based on the cobalt metal). Elemental Analysis: Co3.5C83H59N5O13 (1540.60), Calculated C, 64.70; H, 3.82; N, 4.54; Experimental C, 64.01; H, 3.95; N, 4.71.
2C27H15O6(3-)*C12H12N2*3.5Co(2+)*HO(1-)*2H2O*C3H7NO[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
at 120℃; for 72h;pH 5.4;Autoclave; High pressure;
General procedure: CoCl2 (0.25 mmol), 1,3,5-Tris(4-carboxyphenyl)benzene (BTB) (0.05 mmol) and 1,2-bis (4-pyridyl) ethane (0.10 mmol) were dissolved in 10 mL of solvent mixture (6 mL milli-Q water + 4 mL DMF) and its pH was 4.9. This solution was sonicated for 5 min and then transferred into a Parr Teflon-lined vessel (23 mL). The vessel was sealed in an autoclave and heated at 120C for 3 days in a programmable oven. Purple coloured needle-shaped crystals of compound 1 were formed. Crystals were washed with milli-Q water and dried under vacuum for further use. The yield of compound 1 is 60% (based on the cobalt metal).
C27H15O6(3-)*1.5Co(2+)*H2O*C3H7NO*C16H12N2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
at 120℃; for 72h;pH 5;Autoclave; High pressure;
CoCl2 (0.2 mmol), 1,3,5-Tris (4-carboxyphenyl) benzene (0.05 mmol) [BTB], 1,4-Di(4-pyridyl)benzene (0.05 mmol) [DPB] were dissolved in the solvent mixture (6 mL milli-Q water + 4 mL DMF) and it's pH was 5.0. This reaction mixture was sonicated for 5 min then transferred into a Parr Teflon-lined vessel (23 mL). The vessel was sealed in an autoclave then heated at 120°C for 3 days in a programmable oven. Purple coloured needle-shaped crystals of compound 3 were formed. Crystals were washed with milli-Q water and dried under vacuum for further use. Elemental Analysis: The yield of compound 3 is 92percent (based on the cobalt metal). Elemental Analysis: Co1.5C46H29N3O8 (840.00), Calculated C, 65.75; H, 3.45; N, 3.52; Experimental C, 65.01; H, 3.70; N, 3.61.
In N,N-dimethyl-formamide; at 150℃; for 72h;High pressure; Autoclave;
General procedure: Solvothermal reaction of H3BTB (0.1 mmol) and Ln(NO3)36H2O(0.1 mmol; Ln = Eu (1), Dy (2)) was performed in a mixture solvents of DMF (5 mL) and H2O (2 mL) in a 15 mL Teflon-lined stainless steel autoclave, which was heated at 150 C for 3 days and then cooled to room temperature at 1.5 C/h. Colourless needle shaped crystals were filtered out and washed with DMF and H2O three times. [Eu(BTB)(H2O)]n (1). Yield based on Eu: 44%.
Cd(tri(4-imidazolylphenyl)amine)(HBTB)•H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
48%
In N,N-dimethyl-formamide; at 120℃; for 72h;Autoclave; High pressure;
General procedure: A mixture containing CdI2 (36.6mg, 0.1mmol), H2BIPA (24.5mg, 0.1mmol), and TIPA (44.3mg, 0.1mmol) in DMF/H2O (1:1, v/v) solution (10ml) was sealed in a Teflon-lined stainless steel container and heated at 120C for 3days. After being cooled down to room temperature, colorless block crystals of 1 were obtained in 42% yield based on TIPA.
[Mg3(4,4',4''-benzene-1,3,5-triyl-tribenzoate)2(DMA)4]·4DMA·2H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
42%
With magnesium(II) nitrate hexahydrate; In water; at 120℃; for 72h;Autoclave; High pressure;
A mixture of H3BTB (17.6mg, 0.04mmol) and Mg(NO3)2·6H2O (30.8mg, 0.12mmol) in DMA (0.5mL) and H2O (0.05mL) was stirred for 5 min at room temperature. Then the mixture was placed in a 23mL Parr Teflon-lined stainless steel vessel and heated at 120C for 72h. The reaction system was cooled slowly and thick plate-shaped pale yellow crystals of 1 were obtained (yield: 7.0mg, 42% based on H3BTB). Anal. calcd. for C86H106N8Mg3O22: C, 61.60; H, 6.37; N, 6.68%. Found: C, 61.19; H, 6.22; N, 6.63%. IR: 3373 (br, w), 1664 (m), 1587 (m), 1544(m), 1389(s), 1179(m), 1100(m), 856(m), 784(m), 706(m), 665(m) cm-1.
[Mg3(4,4',4''-benzene-1,3,5-triyl-tribenzoate)(CH3COO)3(H2O)3]·3.5DMA·1.5H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
35%
With magnesium(II) nitrate hexahydrate; nitric acid; In water; at 120℃; for 72h;Autoclave; High pressure;
H3BTB (17.6 mg, 0.04 mmol), Mg(NO3)2·6H2O (30.8 mg, 0.12 mmol) and CH3COONH4 (18.4 mg, 0.24 mmol) were mixed in DMA (0.5 mL) and H2O (0.05 mL), and acidified with HNO3 (3M in DMA, 50 mL). The mixture was stirred for 5 min at room temperature. Then it was placed in a 23 mL Parr Teflon-lined stainless steel vessel and heated at 120 C for 72 h. The reaction system was cooled slowly and hexagonal prism-shaped pale yellow crystals of 2 were obtained (7.5 mg, yield 35% based on H3BTB). Anal. Calcd. for C47H64.5N3.5Mg3O20: C, 52.69; H, 6.07; N, 4.58%. Found: C, 52.42; H, 5.78; N, 4.25%. IR: 3396 (br, w), 1608 (s), 1555 (m), 1415(s), 1182(w), 1016(w), 856(w), 789(m), 713(w), 667(m) cm-1.
A mixture of In(NO3)23H2O (30.5 mg, 0.1 mmol) and H3BTB (50.0 mg, 0.15 mmol) in10 mL DMF/H2O (V/V8:2) as solvent was transferred into a Teflon-lined autoclave,sealed and placed in a preheated electric oven at 120 C for 72 h. Colorless crystals of2 were collected and washed with DMF three times. Elemental analysis calcd (%) for 2(C33H31InN2O9): C, 55.48; H, 4.37; N, 3.92; found: C, 55.62; H, 4.07; N, 4.11.
A mixture of La(NO3)36H2O (43 mg, 0.1 mmol,), H3BTB (0.2 mmol), H2O (2.0 mL) and DMF (3.0 mL) was sealed ina Teflon-lined stainless steel autoclave (25.0 mL) and heated at 130 C for 2 days, then increased to 170 C and maintained at this temperature for 3 days. After the autoclave had cooled automatically to room temperature over 10 h, X-ray qualified colorless crystals of 1 were harvested. These crystals were washed with water and dried in air. Elemental analysis calcd (%) for 1 (C27H17LaO8): C, 54.75; H, 2.89; found: C, 54.71; H, 3.09. IR for 1: 3386 m, 1924 m, 1561 s,1502 s, 1358 s, 1166 m, 1016 m, 895 m, 776 s cm1
With hydrogenchloride; In methanol; at 160℃; for 72h;Autoclave; High pressure;
For 1, Ho(NO3)36H2O (0.05 mmol), H3BTB (0.05 mmol, 0.022 g), dilute HCl (0.2 mL, 0.01M), distilled H2O (10 mL) and CH3OH (5 mL) were sealed in a 25-mL Teflon-liner autoclave,heated in an oven at 160 C for 72 h under autogenous pressure to produceblock crystals in quantitative yield. The pH values in the solution are in the range 5-6.The cube-shape crystals of 1 were collected by filtration, washed with distilled waterand ethanol, and dried at room temperature (yield 45% based on the H3BTB ligand).Anal. Calc. for C36H42N6O24S6Ho2: C, 29.83; H, 2.92; N, 5.80%. Found: C, 30.12; H, 2.22;N, 5.89%. IR (KBr, cm1): 3454(w), 3116(w), 1553(s), 1519(s), 1384(s), 1240(s), 1123(m),1067(s), 1015(w), 964(w), 930(w), 855(m), 824(s), 745(s), 653(m), 531(m).
MOF-520, Al8(OH)8(HCOO)4BTB4. In a 20 mL scintillation vial, the mixture solution of Al(NO3)3.9H2O (90.0 mg, 0.240 mmol), H3BTB (75.0 mg, 0.170 mmol) in DMF (17 mL) was prepared. The solution was sonicated for 1 min and formic acid (1.40 mL, 0.0310 mol) was added to the solution. The vial was capped and placed in the preheated 140 C. oven. After 4 days, block shaped clear single crystals with size range 50 to 100 mum were obtained on the wall of the vial. Subtle temperature difference can affect the quality of the single crystals. It is recommended that several vials containing the solution be set together and placed in different locations in the oven. The vial with the best single crystals was chosen and the single crystals were used for the inclusion of the molecules. For the characterization of MOF-520, the rest of the crystals were further processed.
With 2,6-dimethylpyridine; at 120℃; for 72h;Sealed tube; High pressure;
We added the mixture of H3BTB (0.062 mmol, 35 mg) andGd(NO3)36H2O (0.1 mmol, 46 mg) into a solution of H2O (1 mL)and DMF (4 mL). After joining 3 drops of 2,6-lutidine, sealing themixture in the Pyrex tube, and then heated them for three days atone hundred twenty centigrade degree. Since they were cooled toroom temperature, we filtered the light yellow polyhedral-shapedcrystals formed, and washed them with H2O, last, we dried themin the air. Compound 1's analytical found (C30H23GdNO9): N, 2.24%;H, 3.19%; C, 51.66%. Calculate: N, 2.00%; H, 3.32%; C, 51.57%.
catena-[bis(μ-1,3,5-tris(4-carboxylatophenyl)benzene)-(μ-hydrate)-trizinchepta-N,N-dimethylformamide solvate][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With nitric acid; at 90℃; for 72h;
A mixture of 1,3,5-tris(4-carboxyphenyl)benzene (H3BTB) (15.4 mg, 0.035 mmol) wasadded to 3mL of 1:1 (v/v) H2O/dimethylformamide (DMF) solution, then Zn(NO3)2 6H2O(40.2 mg, 0.135 mmol) and three drops of concentrated nitric acid were added. The solutionswere mixed well in a 20mL glass scintillation vial, and then heated to 90 and keptat that temperature for 3 days. After cooling slowly to room temperature, colorless blockcrystals were isolated with 36% yield (10 mg) based on H3BTB. Anal. Calcd (%) for 1C75H83N7O21Zn3: C, 55.79; H, 5.18; N, 6.07%. Found: C, 55.91; H, 5.42; N, 6.24%. ProminentFT-IR peaks for 1 (KBr pellet, cm1): 3468(m), 2965(m), 2874(m), 2322(w), 2302(w),1612(s), 1472(m), 1369(m), 1121(s), 1019(m), 934(s), 817(s), 779(s), 708(m).
N4,N4??-bis((tert-butyldiphenylsilyl)oxy)-5?-(4-(((tert-butyldi&No.x;FFFE;phenylsilyl)oxy)carbamoyl)phenyl)-[1,1?:3?,1??-terphenyl]-4,4??-dicarboxamide[ No CAS ]
With water; calcium chloride; at 120℃; for 120h;Autoclave;
The synthesis of complex 1 follows a modified synthesisoperation reported in the literature [17]. H3BTB (0.050 g, 0.115 mmol), CaCl2 (0.034 g, 0.30 mmol), N-methyl-pyrrolidone(7.5 g) and H2O (1.5 g) were mixed and the mixture was stirred for half an hour. The resulting homogeneous mixture wasthen transferred to a 25 mL Teflon-lined stainless steel autoclave and heated at 120 C for five days. Needle-like colorlesscrystals were obtained upon cooling the mixture to room temperature as described above. Yield: 82% based on H3BTB used.Analytically found for compound 1 (C69H69Ca3N3O21), %: C 59.12, H 5.03, N 2.96. Calculated, %: C 59.34, H 4.98, N 3.01.FT-IR (cm-1): 3258 (w), 3054 (w, br), 1628 (s), 1539 (m), 1418 (s), 1379 (s), 1355 (s), 1211 (m), 1121 (m), 1024 (m),900 (w), 799 (s), 774 (m), 709 (m), 693 (s), 629 (m).
1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene[ No CAS ]
[ 50446-44-1 ]
[ 68-12-2 ]
C27H16O6(2-)*C27H18N6*Zn(2+)*2C3H7NO*H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
at 80℃; for 48h;Autoclave; High pressure;
In a cleaned Teflon-lined stainless steel autoclave a mixture of ZnCl2·6H2O (40 mg, 0.163 mmol), TBIB (17.3 mg, 0.040 mmol),H3TCPB (17.52 mg, 0.040 mmol) and solvent DMF:H2O (3 ml,2:1 v/v) was placed. Heating was done up to 80 C for 48 h under autogenous pressure followed by cooling down to room temperatureat a rate of 10 C/h. Colourless crystals of the polymer was obtained and washed with DMF followed by acetone. Yield 90%.Anal. Calcd for C60H50N8O9Zn = C, 65.90; H, 4.57; N, 10.25%. Found:C, 66.0; H, 4.61; N, 10.22%. FT-IR (KBr pellets, cm-1): 3426, 1671,1607, 1499, 1384, 1299, 1248, 773 (Fig. 3b).
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