2024年4月26日发(作者：厍琪)
序
号
1
配体 条件
ZrOCl2.8H2O (200 mg), H3TATB (60 mg) and 0.6mL
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
结构
PCN-777
来源
Angew. Chem. Int. Ed. 2014,
53, 1 – 7
2
All samples were synthesized via a reflux
method involving the reaction of 2-sulfoterephthalic
acid with ZrCl
4
in water under relatively concentrated
conditions. For the sample with no additives during
synthesis (1), monosodium 2-sulfoterephthalic acid (5
g, 18.6 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
4
(2.5 g, 10.7 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,
DOI: 10.1021/jacs.5b07267
J. Am. Chem. Soc. XXXX, XXX,
XXX−XXX
3
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.
Synthesis of 14 nm UiO-66-N3 (Zr6O4OH4(C8H3O4-N3)6
纳米 级别
2-Azido-1,4-benzenedicarboxylic acid (50 mg, 0.24 mmol)
was dissolved in 1 mL
of N,N Dimethylformamide (DMF). In a separate vial,
zirconyl chloride octahydrate (21
mg, 0.066 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
/10.1021/ja503215w | J.
Am. Chem. Soc. 2014, 136, 7261
−7264
4
DUT-67. ZrCl
4
/HfCl
4
(230 mg/320 mg, 1 mmol)
was dissolved in the mixture of DMF (12.5 mL) and NMP (12.5
mL) by sonication for 10 min. 2,5-Thiophenedicarboxylic acid
/10.1021/cg301691d |
Cryst. Growth Des. 2013, 13,
1231−1237
(H
2
tdc) (110 mg, 0.67 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 (71.5%) for DUT-67(Zr) and 259
mg
(63.9%) 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
4
/HfCl
4
(230 mg/320 mg, 1 mmol)
was dissolved in DMF (25 mL) by sonication for 10 min. H
2
tdc
(258 mg, 1.5 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 (53.9%) for DUT-67(Zr) and 453 mg (52.3%) 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 solutionofH
2
eddb (65mg,0.24mmol),ZrCl
4
(60 mg,
JournalofSolidStateChemistry223(20
15)104–108
0.25mmol),2.5mLofaceticacid(HOAc)in16mLof
formamide(DMF)wassealedina20mLglassvialandheatedat
ultingcolorlesscrystalswerecollectedand
washedwithDMFandacetone,andthendriedinair(yield72mg).
N,N-dimethyl-
120 1C
ZrCl
4
(24 mg) was dissolved in 8 mL of
N,N-dimethylformamide (DMF) in a 25 mL pyrex vial,
to which 1.0g benzoic acid was added. The mixture
was heated in 85 ºC oven for 1 hours and cooled
to the room temperature. Then, H
6
TBPP (20 mg)
was added to the above solution, which was
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: 38.89% based on
Chem. Sci., 2015, 6,
3466–3470 |
3467
H
6
TBPP). 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
[Zr
6
O
4
(OH)
4
(H
2
TBPP)
3
]
n
·~20nH
2
O):
UiO-66a
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/ 1.6
ml HAc under 5 min sonication. Terephthalic acid
(0.136 g, 0.82 mmol, 1.1 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 12 h at RT followed by 12 h
at
120C (ramp 1C/min).
UiO-66b
0.24 g ZrOCl
2
*8H
2
O was dissolved in 32 ml DMF/ 3 g
benzoic acid under 5 min sonication. Terephthalic
acid (0.136 g, 0.82 mmol, 1.1 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 –
0.15 g.
UiO-66f
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/ 0.8
ml HCOOH under 5 min sonication. Terephthalic
acid (0.136 g, 0.82 mmol, 1.1 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 12 h at RT followed by 12 h
at
120C (ramp 1C/min). Yield of the activated material
– 0.12 g.
UiO-66h
0.528 g ZrOCl
2
*8H
2
O was dissolved in 40 ml DMF/
1.4 ml (10 eq) HCl under 5 min sonication.
Terephthalic acid (0.272 g, 1.64 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/NEt
3
/H
2
O
(20/0.4/0.4 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 – 0.36 g.
UiO-67a
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/ 1.6
ml HAc under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.198 g, 0.82 mmol, 1.1
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 – 0.19 g.
S4
UiO-67b
0.24 g ZrOCl
2
*8H
2
O was dissolved in 32 ml DMF/ 3 g
benzoic acid under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.198 g, 0.82 mmol, 1.1
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 – 0.16 g.
UiO-67f
1.2 g ZrOCl
2
*8H
2
O 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 – 0.95 g.
UiO-67h
0.528 g ZrOCl
2
*8H
2
O was dissolved in 40 ml DMF/
1.4 ml (10 eq) HCl under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.396 g, 1.64 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/NEt
3
/H
2
O (20/0.4/0.4 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 –
0.38 g.
UiO-67t
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/
0.16 ml TFA under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.198 g, 0.82 mmol, 1.1
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 – 0.1 g.
UiO-68a
0.12 g ZrOCl
2
*8H
2
O was dissolved in 10 ml DMF/ 0.8
ml HAc under 5 min sonication.
2',5'-dimethyl-[pterphenyl]-
4,4''-dicarboxylic acid (0.128 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 – 0.13 g.
UiO-68b
0.132 g ZrOCl
2
*8H
2
O was dissolved in 16 ml DMF/
1.5 g benzoic acid under 5 min sonication. 2',5'-
dimethyl-[p-terphenyl]-4,4''-dicarboxylic acid (0.142
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 – 0.06 g.
S5
UiO-67Cr
53 mg of CrCl
3
*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 CrCl
3
*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 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
26
)
3
Zirconyl chloride octahydrate (12.5 mg, 0.037
mmol) was added to N,N-dimethylformamide (DMF,
10 mL) and sonicated for thirty minutes. Following
sonication, tetrakis(4-carboxyphenyl)porphyrin (2.5
mg, 0.037 mmol) was added to the solution. After
ten minutes further sonication, acetic acid (2.5 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 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
24
Cu)
3
Zirconyl chloride octahydrate (12.5 mg, 0.037
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication, Cu(II)
meso-tetra(4-carboxyphenyl)porphyrin (2.5 mg,
0.037 mmol) was added to the solution. After ten
/10.1021/ic300825s |
Inorg. Chem. 2012, 51, 6443−
6445
minutes further sonication, acetic acid (2.5 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 Zr
6
O
4
(OH)
4
(C
36
O
8
H
20
)
3
Zirconium tetrachloride (5.6 mg, 0.024 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)
(H
4
-XF, 16 mg, 0.024 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 Zr
6
(H
2
O)
8
O
8
(C
48
N
4
O
8
H
26
)
2
Zirconyl chloride octahydrate (37.5 mg, 0.111
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication,
tetrakis(4-carboxyphenyl)porphyrin (6.5 mg, 0.037
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 Zr
6
(H
2
O)
8
O
4
(C
48
N
4
O
8
H
24
FeCl)
2
Zirconyl chloride octahydrate (37.5 mg, 0.111
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication, Fe(III)
meso-tetra(4-carboxyphenyl)porphyrin chloride (6.5
mg, 0.037 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 Zr
6
(H
2
O)
8
O
4
(C
48
N
4
O
8
H
24
Cu)
2
Zirconyl chloride octahydrate (37.5 mg, 0.111
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication, Cu(II)
meso-tetra(4-carboxyphenyl)porphyrin (6.5 mg,
0.037 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 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
24
Fe)
3
Iron chloride FeCl
3
(100 mg, 0.62 mmol) was
dissolved in to DMF (10 mL). To the solution was
added MOF-525 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
26
)
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.
DOI:
10.1021/hem.5b01053
Inorg. Chem. X
2024年4月26日发(作者：厍琪)
序
号
1
配体 条件
ZrOCl2.8H2O (200 mg), H3TATB (60 mg) and 0.6mL
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
结构
PCN-777
来源
Angew. Chem. Int. Ed. 2014,
53, 1 – 7
2
All samples were synthesized via a reflux
method involving the reaction of 2-sulfoterephthalic
acid with ZrCl
4
in water under relatively concentrated
conditions. For the sample with no additives during
synthesis (1), monosodium 2-sulfoterephthalic acid (5
g, 18.6 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
4
(2.5 g, 10.7 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,
DOI: 10.1021/jacs.5b07267
J. Am. Chem. Soc. XXXX, XXX,
XXX−XXX
3
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.
Synthesis of 14 nm UiO-66-N3 (Zr6O4OH4(C8H3O4-N3)6
纳米 级别
2-Azido-1,4-benzenedicarboxylic acid (50 mg, 0.24 mmol)
was dissolved in 1 mL
of N,N Dimethylformamide (DMF). In a separate vial,
zirconyl chloride octahydrate (21
mg, 0.066 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
/10.1021/ja503215w | J.
Am. Chem. Soc. 2014, 136, 7261
−7264
4
DUT-67. ZrCl
4
/HfCl
4
(230 mg/320 mg, 1 mmol)
was dissolved in the mixture of DMF (12.5 mL) and NMP (12.5
mL) by sonication for 10 min. 2,5-Thiophenedicarboxylic acid
/10.1021/cg301691d |
Cryst. Growth Des. 2013, 13,
1231−1237
(H
2
tdc) (110 mg, 0.67 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 (71.5%) for DUT-67(Zr) and 259
mg
(63.9%) 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
4
/HfCl
4
(230 mg/320 mg, 1 mmol)
was dissolved in DMF (25 mL) by sonication for 10 min. H
2
tdc
(258 mg, 1.5 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 (53.9%) for DUT-67(Zr) and 453 mg (52.3%) 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 solutionofH
2
eddb (65mg,0.24mmol),ZrCl
4
(60 mg,
JournalofSolidStateChemistry223(20
15)104–108
0.25mmol),2.5mLofaceticacid(HOAc)in16mLof
formamide(DMF)wassealedina20mLglassvialandheatedat
ultingcolorlesscrystalswerecollectedand
washedwithDMFandacetone,andthendriedinair(yield72mg).
N,N-dimethyl-
120 1C
ZrCl
4
(24 mg) was dissolved in 8 mL of
N,N-dimethylformamide (DMF) in a 25 mL pyrex vial,
to which 1.0g benzoic acid was added. The mixture
was heated in 85 ºC oven for 1 hours and cooled
to the room temperature. Then, H
6
TBPP (20 mg)
was added to the above solution, which was
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: 38.89% based on
Chem. Sci., 2015, 6,
3466–3470 |
3467
H
6
TBPP). 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
[Zr
6
O
4
(OH)
4
(H
2
TBPP)
3
]
n
·~20nH
2
O):
UiO-66a
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/ 1.6
ml HAc under 5 min sonication. Terephthalic acid
(0.136 g, 0.82 mmol, 1.1 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 12 h at RT followed by 12 h
at
120C (ramp 1C/min).
UiO-66b
0.24 g ZrOCl
2
*8H
2
O was dissolved in 32 ml DMF/ 3 g
benzoic acid under 5 min sonication. Terephthalic
acid (0.136 g, 0.82 mmol, 1.1 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 –
0.15 g.
UiO-66f
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/ 0.8
ml HCOOH under 5 min sonication. Terephthalic
acid (0.136 g, 0.82 mmol, 1.1 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 12 h at RT followed by 12 h
at
120C (ramp 1C/min). Yield of the activated material
– 0.12 g.
UiO-66h
0.528 g ZrOCl
2
*8H
2
O was dissolved in 40 ml DMF/
1.4 ml (10 eq) HCl under 5 min sonication.
Terephthalic acid (0.272 g, 1.64 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/NEt
3
/H
2
O
(20/0.4/0.4 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 – 0.36 g.
UiO-67a
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/ 1.6
ml HAc under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.198 g, 0.82 mmol, 1.1
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 – 0.19 g.
S4
UiO-67b
0.24 g ZrOCl
2
*8H
2
O was dissolved in 32 ml DMF/ 3 g
benzoic acid under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.198 g, 0.82 mmol, 1.1
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 – 0.16 g.
UiO-67f
1.2 g ZrOCl
2
*8H
2
O 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 – 0.95 g.
UiO-67h
0.528 g ZrOCl
2
*8H
2
O was dissolved in 40 ml DMF/
1.4 ml (10 eq) HCl under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.396 g, 1.64 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/NEt
3
/H
2
O (20/0.4/0.4 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 –
0.38 g.
UiO-67t
0.24 g ZrOCl
2
*8H
2
O was dissolved in 20 ml DMF/
0.16 ml TFA under 5 min sonication. 4,4′-
biphenyldicarboxylic acid (0.198 g, 0.82 mmol, 1.1
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 – 0.1 g.
UiO-68a
0.12 g ZrOCl
2
*8H
2
O was dissolved in 10 ml DMF/ 0.8
ml HAc under 5 min sonication.
2',5'-dimethyl-[pterphenyl]-
4,4''-dicarboxylic acid (0.128 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 – 0.13 g.
UiO-68b
0.132 g ZrOCl
2
*8H
2
O was dissolved in 16 ml DMF/
1.5 g benzoic acid under 5 min sonication. 2',5'-
dimethyl-[p-terphenyl]-4,4''-dicarboxylic acid (0.142
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 – 0.06 g.
S5
UiO-67Cr
53 mg of CrCl
3
*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 CrCl
3
*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 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
26
)
3
Zirconyl chloride octahydrate (12.5 mg, 0.037
mmol) was added to N,N-dimethylformamide (DMF,
10 mL) and sonicated for thirty minutes. Following
sonication, tetrakis(4-carboxyphenyl)porphyrin (2.5
mg, 0.037 mmol) was added to the solution. After
ten minutes further sonication, acetic acid (2.5 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 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
24
Cu)
3
Zirconyl chloride octahydrate (12.5 mg, 0.037
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication, Cu(II)
meso-tetra(4-carboxyphenyl)porphyrin (2.5 mg,
0.037 mmol) was added to the solution. After ten
/10.1021/ic300825s |
Inorg. Chem. 2012, 51, 6443−
6445
minutes further sonication, acetic acid (2.5 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 Zr
6
O
4
(OH)
4
(C
36
O
8
H
20
)
3
Zirconium tetrachloride (5.6 mg, 0.024 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)
(H
4
-XF, 16 mg, 0.024 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 Zr
6
(H
2
O)
8
O
8
(C
48
N
4
O
8
H
26
)
2
Zirconyl chloride octahydrate (37.5 mg, 0.111
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication,
tetrakis(4-carboxyphenyl)porphyrin (6.5 mg, 0.037
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 Zr
6
(H
2
O)
8
O
4
(C
48
N
4
O
8
H
24
FeCl)
2
Zirconyl chloride octahydrate (37.5 mg, 0.111
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication, Fe(III)
meso-tetra(4-carboxyphenyl)porphyrin chloride (6.5
mg, 0.037 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 Zr
6
(H
2
O)
8
O
4
(C
48
N
4
O
8
H
24
Cu)
2
Zirconyl chloride octahydrate (37.5 mg, 0.111
mmol) was added to DMF (10 mL) and sonicated for
thirty minutes. Following sonication, Cu(II)
meso-tetra(4-carboxyphenyl)porphyrin (6.5 mg,
0.037 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 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
24
Fe)
3
Iron chloride FeCl
3
(100 mg, 0.62 mmol) was
dissolved in to DMF (10 mL). To the solution was
added MOF-525 Zr
6
(OH)
4
O
4
(C
48
N
4
O
8
H
26
)
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.
DOI:
10.1021/hem.5b01053
Inorg. Chem. X