序号 1 配体 条件 结构 来源 (200 mg), H3TATB (60 mg) and trifluoroacetic acid in 12 mL of DEF were ultrasonically dissolved in a Pyrex vial. The mixture was heated at 120 ºC in an oven for 12 h. After cooling down to room temperature, white powder crystalline precipitate was harvested by filtration · 2 All samples were synthesized via a reflux ( method involving the reaction of 2-sulfoterephthalic acid with ZrClin water under relatively concentrated conditions. For the sample with no additives during synthesis (1), monosodium 2-sulfoterephthalic acid (5 g, mmol) was dissolved in minimal water, and then passed through DOWEX 50WX8 proton exchange resin to obtain 2-sulfoterephthalic acid. The water was then removed by rotary evaporation,
then 40 mL of fresh ultrapure water was added to dissolve the solid. Separately, ZrCl g, mmol) was dissolved in 15 mL of ultrapure water (caution, highly exothermic), then the two solutions were mixed to make a clear, slightly pink solution with pH < 1. The solution was then heated to reflux, and after ~3 minutes a white precipitate formed. Reflux was continued for 16 hours, then the solution was cooled and the solid was recovered by centrifugation. The solid was then washed 2x with ultrapure water, then refluxed for another 16 hours in ultrapure water to purify. 3 Synthesis of 14 nm UiO-66-N3 纳米 级别 (Zr6O4OH4(C8H3O4-N3)6 2-Azido-1,4-benzenedicarboxylic acid (50 mg, mmol) was dissolved in 1 mL of N,N Dimethylformamide (DMF). In a separate vial, zirconyl chloride octahydrate (21
' mg, mmol) was dissolved in 3 mL of DMF. The two solutions were mixed together in a 10 mL scintillation vial, and acetic acid (300 µl) was added to the reaction mixture. The solution was heated at 90 ˚C for 18 h to yield UiO-66-N3 (Zr6O4OH4(C8H3O4-N3)6. MOF nanoparticles were purified by centrifugation (15000 rpm, 90 min) followed by solvent exchange (3 x DMF and 3 x NANOpure H2O) over a 48 h period. MOF nanoparticles were suspended in H2O for characterization and functionalization with ~ DUT-67. ZrCl/HfCl(230 mg/320 mg, 1 mmol) was dissolved in the mixture of DMF mL) and NMP mL) by * 4 sonication for 10 min. 2,5-Thiophenedicarboxylic acid (Htdc) (110 mg, mmol) was added to resulting solution and sonicated additional 5 min. After that acetic acid (7 mL,
117 mmol) was added to the solution and sonicated for 10 min. The resulting mixture was distributed to 10 Pyrex tubes, which were subsequently tempered at 120 °C for 48 h. The resulted powder was separated by centrifugation and washed several times with DMF until supernatant solution became colorless. The powder was filtered and dried under argon atmosphere for half an hour. Yield: 224 mg %) for DUT-67(Zr) and 259 mg %) for DUT-67(Hf). The single crystals of DUT-67 were obtained using the same procedure, but 10 mL of acetic acid instead of 7 mL were added. 5 ZrCl/HfCl(230 mg/320 mg, 1 mmol) was dissolved in DMF (25 mL) by sonication for 10 min. Htdc (258 mg, mmol) was added to resulting solution, and the mixture was sonicated additional 5 min. After that acetic acid (11 mL, 183 mmol) was added and the mixture was sonicated for further 10 min. The reaction mixture was .
distributed to 12 Pyrex tubes, which were subsequently tempered at 120 °C for 72 h. The washing and drying procedure was the same as applied to DUT-67. Yield: 384 mg %) for DUT-67(Zr) and 453 mg %) for DUT-67(Hf). The single crystals of DUT-68(Zr) were obtained using the same synthetic protocol, but utilizing larger amount of modulator.
} A solutionofHeddb (65mg,,ZrCl(60 mg, ,(HOAc)in16mLof N,N-dimethyl- formamide(DMF)wassealedina20mLglassvialandheatedat 120 1C washedwithDMFandacetone,andthendriedinair(yield72mg). ZrCl(24 mg) was dissolved in 8 mL of N,N-dimethylformamide (DMF) in a 25 mL pyrex vial, to which benzoic acid was added. The mixture was heated in 85 ºC oven for 1 hours and cooled to the room temperature. Then, HTBPP (20 mg) was added to the above solution, which was {Chem. Sci., 2015, 6, 3466–3470 | 3467 sonicated for a while. The resulting mixture was heated in 120 ºC oven for 96 hours to yield about 14 mg of dark red crystals (yield: % based on HTBPP). The crystals obtained were filtered and washed with DMF. Elemental analyses calcd (%)
for FJI-H6 (After activation and absorbed small amount of water, the crystal has a formula of [ZrO(OH)(HTBPP)]·~20nHO): & ： UiO-66a g ZrOCl2*8H2O was dissolved in 20 ml DMF/ ml HAc under 5 min sonication. Terephthalic acid g, mmol, eq) was added and the mixture was
sonicated for 5 min more and placed into 120C preheated oven for 1 day. Solution was decanted/centrifuged, precipitate was washed DMF 4 times and acetone 4 times over 12 hours. The material was evacuated 12 h at RT followed by 12 h at 120C (ramp 1C/min). UiO-66b · g ZrOCl2*8H2O was dissolved in 32 ml DMF/ 3 g benzoic acid under 5 min sonication. Terephthalic acid g, mmol, eq) was added and the mixture was sonicated for 5 min more, distributed to 4 vials and placed into 120C preheated oven for 1 day. Precipitate was filtered, washed
DMF 4 times and acetone 4 times over 12 hours. The material was evacuated 12 h at RT followed by 12 h at 120C (ramp 1C/min). Yield of the activated material – g. UiO-66f g ZrOCl2*8H2O was dissolved in 20 ml DMF/ ml HCOOH under 5 min sonication. Terephthalic acid g, mmol, eq) was added and the mixture was sonicated for 5 min more and placed [ into 120C preheated oven for 1 day. Solution was decanted/centrifuged, precipitate was washed DMF 4 times and acetone 4 times over 12 hours. The material was evacuated 12 h at RT followed by
12 h at 120C (ramp 1C/min). Yield of the activated material – g. UiO-66h g ZrOCl2*8H2O was dissolved in 40 ml DMF/ ml (10 eq) HCl under 5 min sonication. Terephthalic acid g, mmol, 1 eq) was added and the mixture was sonicated for 5 min more and placed into 120C preheated oven for 1 day. Precipitate was filtered, washed DMF, DMF/NEt3/H2O (20/ ml), DMF 2 times and acetone 4 times over 6 hours. The material was evacuated 4 h at 70C @ followed with 15h at 150C (ramp 1C/min). Yield of the activated material – g. UiO-67a
g ZrOCl2*8H2O was dissolved in 20 ml DMF/ ml HAc under 5 min sonication. 4,4′- biphenyldicarboxylic acid g, mmol, eq) was added and the mixture was sonicated for 5 min more and placed into 120C preheated oven for 1 day. Solution was decanted/centrifuged, precipitate was washed DMF 4 times and acetone 4 times over 12 hours. The material was evacuated 19 h at RT followed by 6 h at 100C (ramp 1C/min). Yield of the activated material – g. S4 ： UiO-67b g ZrOCl2*8H2O was dissolved in 32 ml DMF/ 3
g benzoic acid under 5 min sonication. 4,4′- biphenyldicarboxylic acid g, mmol, eq) was added and the mixture was sonicated for 5 min more, distributed to 4 vials and placed into 120C preheated oven for 1 day. Precipitated was filtered, washed DMF 4 times and acetone 4 times over 12 hours. The material was evacuated 19 h at RT followed by 6 h at 100C (ramp 1C/min). Yield of the activated material – g. UiO-67f g ZrOCl2*8H2O was dissolved in 100 ml DMF/ 4 ml HCOOH under 5 min sonication. 4,4′- （ biphenyldicarboxylic acid (1 g) was added and the mixture was sonicated for 5 min more and
placed into 120C preheated oven for 1 day. Precipitate was fine-filtered/centrifuged, washed DMF 4 times and acetone 5 times over 4 hours. To remove solvents from pores the material was evacuated 12 h at RT followed with 12 h at 120C (ramp 1C/min). Yield of the activated material – g. UiO-67h g ZrOCl2*8H2O was dissolved in 40 ml DMF/ ml (10 eq) HCl under 5 min sonication. 4,4′- biphenyldicarboxylic acid g, mmol, 1 eq) was added and the mixture was sonicated for 5 min more and placed into 120C preheated oven for 1 day. Precipitate was filtered, washed DMF,
# DMF/NEt3/H2O (20/ ml), DMF 2 times and acetone 4 times over 6 hours. The material was evacuated 4 h at 70C followed with 15h at 120C (ramp 1C/min). Yield of the activated material – g. UiO-67t g ZrOCl2*8H2O was dissolved in 20 ml DMF/ ml TFA under 5 min sonication. 4,4′- biphenyldicarboxylic acid g, mmol, eq) was added and the mixture was sonicated for 5 min more and placed into 120C preheated oven for 1 day. Solution was decanted/centrifuged, precipitate was washed DMF 4 times and acetone 4 times over 12 hours. The material was evacuated
19 h at RT followed by 6 h at 100C (ramp 1C/min). Yield of the activated material – g. # UiO-68a g ZrOCl2*8H2O was dissolved in 10 ml DMF/ ml HAc under 5 min sonication. 2',5'-dimethyl-[pterphenyl]- 4,4''-dicarboxylic acid g, 1 eq) was added and the mixture was sonicated for 5 min more and placed into 120C preheated oven for 1 day. Solution was decanted/centrifuged, precipitate was washed DMF 4 times and acetone 4 times over 12 hours. The material was evacuated 19 h at RT followed by 6 h at 100C (ramp 1C/min). Yield of the activated material – g.
UiO-68b g ZrOCl2*8H2O was dissolved in 16 ml DMF/ g benzoic acid under 5 min sonication. 2',5'- } dimethyl-[p-terphenyl]-4,4''-dicarboxylic acid g) was added and the mixture was sonicated for 5 min more, distributed to 2 vials and placed into 120C preheated oven for 1 day. Precipitate was filtered, washed DMF 4 times and acetone 4 times over 12 hours. The material was evacuated 19 h at RT followed by 6 h at 100C (ramp 1C/min). Yield of the activated material – g. S5 UiO-67Cr 53 mg of CrCl3*3THF was dissolved in 8 ml DCM
and filtered. 50 mg of activated UiO-67f was added to the solution and soaked overnight. The solution was decanted and precipitate was washed with DCM 5 | times during 1d. The material was evacuated 12 h at RT followed by 6 h at 100C (ramp 1C/min). UiO-66Cr 40 mg of CrCl3*3THF was dissolved in 6 ml DCM and filtered. 64 mg of activated UiO-66F was added to the solution and soaked overnight. The solution was decanted and precipitate was washed with DCM 5 times during 1d. The material was evacuated 12 h at RT followed by 6 h at 100C (ramp
1C/min). ~ MOF-525 Zr6(OH)4O4(C48N4O8H26)3 Zirconyl chloride octahydrate mg, mmol) was added to N,N-dimethylformamide (DMF, 10 mL) and sonicated for thirty minutes. Following sonication, tetrakis(4-carboxyphenyl)porphyrin mg, mmol) was added to the solution. After ten minutes further sonication, acetic acid mL) was added to the solution. The solution was placed in a 20 mL scintillation vial and heated at 65 °C for three days. The microcrystalline powder was filtered and washed with DMF (5 × 10 mL) over a three-hour period. The DMF was then replaced with acetone (5 × 30 mL) over a five-day period. Finally, the volatile acetone was removed by heating at 120 °C under vacuum (30 mTorr) for 48 hrs. MOF-525-Cu Zr6(OH)4O4(C48N4O8H24Cu)3
Zirconyl chloride octahydrate mg, mmol) was added to DMF (10 mL) and sonicated for thirty minutes. Following sonication, Cu(II) meso-tetra(4-carboxyphenyl)porphyrin mg, mmol) was added to the solution. After ten minutes further sonication, acetic acid mL) was added to the solution. The solution was placed in a 20 mL scintillation vial and heated at 65 °C for three days. The microcrystalline powder was filtered and washed with DMF (5 × 10 mL) over a three-hour period. The DMF was then replaced with acetone (5 × 30 mL) over a five-day period. Finally, the volatile acetone was removed by heating at 120 °C under vacuum (30 mTorr) for 48 hrs. S4 MOF-535 Zr6O4(OH)4(C36O8H20)3 Zirconium tetrachloride mg, mmol) and acetic acid (2 mL) were added to DMF (10 mL) and sonicated for thirty minutes in a 20 mL
scintillation vial. 4,4'-((1E,1'E)-(2,5-bis((4-carboxyphenyl)ethynyl)-1,4-phenylene)bis(ethene-2,1-diyl))dibenzoic acid) (H4-XF, 16 mg, mmol) added to the solution and dissolved by sonication. The reaction was heated at 60 °C for 4 hrs, followed by heating at 120 °C for two days. The single crystals were collected by filtration, and washed with DMF (5 × 10 mL) over a three-hour period. The DMF was then replaced with acetone (5 × 30 mL) over a five-day period. Finally, the volatile acetone was removed by heating at 100 °C under vacuum (30 mTorr) for 20 hrs. ) MOF-545 Zr6(H2O)8O8(C48N4O8H26)2 Zirconyl chloride octahydrate mg, mmol) was added to DMF (10 mL) and sonicated for thirty minutes. Following sonication, tetrakis(4-carboxyphenyl)porphyrin mg, mmol) was added to the solution. After a
further ten minutes of sonication, formic acid (7 mL) was added to the solution. The solution was placed in two 20 mL scintillation vials and heated at 130 °C for three days. The single crystals were collected by filtration and washed with DMF (5 × 10 mL) over a three-hour period. The DMF was then replaced with acetone (5 × 30 mL) over a five-day period. Finally, the volatile acetone was removed by heating at 120 °C under vacuum (30 mTorr) for 48 hrs. MOF-545-Fe Zr6(H2O)8O4(C48N4O8H24FeCl)2 Zirconyl chloride octahydrate mg, mmol) was added to DMF (10 mL) and sonicated for thirty minutes. Following sonication, Fe(III) meso-tetra(4-carboxyphenyl)porphyrin chloride mg, mmol) was added to the solution. After a further ten minutes of sonication, formic acid (5 mL) was added to the solution. The solution was placed in two
20 mL scintillation vials and heated at 130 °C for three days. S5 The single crystals were collected by filtration and washed with DMF (5 × 10 mL) over a three-hour period. The DMF was then replaced with acetone (5 × 30 mL) over a five-day period. Finally, the volatile acetone was removed by heating at 120 °C under vacuum (30 mTorr) for 48 hrs. MOF-545 Zr6(H2O)8O4(C48N4O8H24Cu)2 Zirconyl chloride octahydrate mg, mmol) was added to DMF (10 mL) and sonicated for thirty minutes. Following sonication, Cu(II) meso-tetra(4-carboxyphenyl)porphyrin mg, mmol) was added to the solution. After a further ten minutes of sonication, formic acid (6 mL) was added to the solution. The solution was placed in two 20 mL scintillation vials and heated at 130 °C for
three days. The single crystals were collected by filtration and washed with DMF (5 × 10 mL) over a three-hour period. The DMF was then replaced with acetone (5 × 30 mL) over a five-day period. Finally, the volatile acetone was removed by heating at 120 °C under vacuum (30 mTorr) for 48 hrs. Section S3: Postmetalation of MOF-525 to form MOF-525-Fe MOF-525-Fe Zr6(OH)4O4(C48N4O8H24Fe)3 Iron chloride FeCl3 (100 mg, mmol) was dissolved in to DMF (10 mL). To the solution was added MOF-525 Zr6(OH)4O4(C48N4O8H26)3 50 mg, the solution was heated at 100 °C for 18 hrs. The microcrystalline powder were collected by filtration and washed with DMF (5 × 10 mL) over a three-hour period. The DMF was then replaced with acetone (5 × 30 mL) over a five-day period. Finally, the volatile
acetone was removed by heating at 120 °C under vacuum (30 mTorr) for 48 hrs.
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