Inorganic Chemistry
Article
here utilize this synthetic advance to bear on the simple yet
1257 (s), 1242 (s), 1192 (m), 1161 (m), 1115 (s), 1057 (s), 771 (m),
7
29 (m), 706 (m).
Synthesis of Dimethyl 3,3′-Bis(acetylthio)biphenyl-p,p′-
unexplored molecule H DMBPD. In particular, we will
2
describe a Zr(IV)-based single crystal system Zr-DMBPD [or
dicarboxylate (SM3). In a N -filled glovebox, anhydrous AlCl
2
3
UiO-67-(SH) ], isoreticular to the UiO-67 prototype, i.e., Zr-
2
(
3.30 g, 24.8 mmol) and anhydrous toluene (41 mL) were added
to a two-necked, round-bottomed flask charged with SM2 (1.60 g,
.11 mmol). The flask was then taken out of the glovebox and
33
BPD with fcc-arrayed Zr O units, but functionalized with
6
8
well-defined, free-standing thiol arrays. Moreover, UiO-67-
SH) also provides insights into the stability issue when
3
(
2
connected to a nitrogen manifold. After stirring at rt for 2 h, the
mixture was chilled in an ice bath, and acetyl chloride (2.64 mL, 37
compared with the relatively delicate UiO-67 solid and the
very robust Zr-TMBPD crystal [UiO-67-(SCH ) (see Figure
1
mmol) was injected under N protection. The ice bath was removed,
3
4
2
3
4
for TMBPD]), by highlighting the steric origin of the
and the resulting mixture was stirred at rt for 1 h and then poured into
an ice−water bath (200 mL) and extracted with DCM (3 × 100 mL).
The combined organic layer was washed with distilled water (3 × 100
stability of the latter. We will also describe the catalytic activity
of Pd-loaded crystals of UiO-67-(SH) in comparison with the
2
mL), dried over MgSO , evaporated in vacuo, and then subjected to
4
reported system of Zr-DMTBD [UiO-68-(SH) (see Figure 1
2
6
flash column chromatography (eluent: n-hexane/DCM from 2 to 1)
for DMTBD]), as an effort to engineer the spatial
1
to yield a white solid (772 mg, 59.3% based on SM2). H NMR (400
configuration of thiol arrays for modifying materials properties.
MHz, CDCl ) δ = 8.04 (d, J = 8.1 Hz, 2H), 7.80 (d, J = 1.8 Hz, 2H),
3
1
3
7
.69 (dd, J = 8.1, 1.9 Hz, 2H), 3.91 (s, 6H), 2.47 (s, 6H). C NMR
(100 MHz, CDCl ) δ = 192.77 (s), 166.27 (s), 142.53 (s), 135.24 (s),
33.18 (s), 131.61 (s), 129.78 (s), 127.93 (s), 52.49 (s), 30.37 (s).
FT-IR (KBr pellet, v/cm ): 2958 (w), 2924 (w), 1720 (s), 1693 (s),
593 (m), 1473 (w), 1450 (w), 1427 (w), 1358 (w), 1288 (s), 1265
EXPERIMENTAL SECTION
3
■
1
−1
1
(
(
s), 1188 (w), 1122 (s), 1053 (m), 949 (w), 879 (w), 829 (w), 768
w), 694 (w), 629 (m).
Synthesis of Dimethyl 3,3′-Bis(fluoro)biphenyl-p,p′-dicar-
boxylate (SM1). Into a two-necked, round-bottomed flask
containing a magnetic stirring bar, nickel(II) dichloride hexahydrate
Synthesis of 3,3′-Bis(mercapto)biphenyl-p,p′-dicarboxylic
Acid (H DMBPD). SM3 (771 mg, 1.84 mmol) was placed in a
2
(
2.034 g, 8.58 mmol), and PPh (9.0 g, 34.3 mmol) on a nitrogen
3
two-necked, round-bottomed flask fitted with a septum and charged
with a magnetic stirring bar. The flask was evacuated and refilled with
N 3 times to afford N protection, and a deaerated KOH solution
manifold was cannulated deaerated DMF (81 mL; bubbled with N2
for 15 min). The mixture was then stirred to afford a deep blue
solution, into which Zn powder (0.561 g, 8.58 mmol) was added
under nitrogen protection. After heating at 50 °C for 1 h (with
stirring; to give a red mixture), methyl 4-bromo-2-fluorobenzoate (2.0
g, 8.582 mmol) was added, and the reaction mixture was kept at 50
2
2
(
1.3 M, 28 mL in EtOH/H O, v/v = 1:1; bubbled by N for 15 min)
2
2
was then added via cannula. After being heated at 90 °C for 36 h, the
reaction mixture was cooled to rt, and a deaerated HCl (10% in water,
1
6 mL; bubbled with N for 5 min) was injected. The precipitate
2
°
C in N2 atmosphere for another 6 h. After cooling to room
formed was filtered, washed extensively with deionized water, and
temperature (rt), methyl iodide (2.2 mL, 35.34 mmol) was injected,
and the resulting mixture was stirred for 2 h. The mixture was then
poured into distilled water (300 mL), and the precipitate was
collected by suction filtration, washed with distilled water (3 × 100
mL), redissolved in ethyl acetate (EA, 500 mL), dried over anhydrous
dried on a filter paper under suction with a nitrogen steam to afford
1
H DMBPD as a pale yellow solid (542 mg, 96% based on SM3). H
2
NMR (400 MHz, DMSO-d ) δ = 8.02 (d, J = 8.2 Hz, 2H), 7.93 (d, J
6
1
3
=
1.7 Hz, 2H), 7.53 (dd, J = 8.2, 1.7 Hz, 2H). C NMR (100 MHz,
DMSO-d ) δ = 167.78 (s), 142.45 (s), 139.89 (s), 132.48 (s), 129.58
MgSO , and purified by flash column chromatography (eluent: n-
6
4
−1
(s), 126.61 (s), 123.52 (s). FT-IR (KBr pellet, v/cm ): 3063 (s),
hexane/DCM from 1 to 0.5) to yield a white solid (920 mg, 70%
1
2970 (s), 2870 (s), 2858 (s), 2654 (m), 2546 (m), 1678 (vs), 1593
vs), 1554 (m), 1535 (m), 1500 (w), 1473 (m), 1419 (s), 1362 (m),
based on methyl 4-bromo-2-fluorobenzoate). H NMR (400 MHz,
(
CDCl ): δ = 8.02 (t, J = 7.8 Hz, 2H), 7.43 (dd, J = 8.2, 1.7 Hz, 2H),
3
1
9
1311 (s), 1257 (vs), 1153 (m), 1061 (m), 922 (w), 876 (m), 833
(m), 810 (m), 771 (m). Chemical analysis of the product yielded the
following: Calcd [C (54.89%), H (3.29%)]. Found [C (53.79%), H
7
.36 (dd, J = 11.6, 1.6 Hz, 2H), 3.95 (s, 6H). F NMR (376 MHz,
1
3
CDCl ): δ = −108.26 (s). C NMR (100 MHz, CDCl ) δ = 164.54
3
3
(
1
d, J = 3.9 Hz), 163.57 (s), 160.98 (s), 144.97 (dd, J = 8.6, 1.8 Hz),
33.04 (d, J = 1.3 Hz), 122.68 (d, J = 3.6 Hz), 118.54 (d, J = 10.2
(
3.27%)].
−
1
Preparation of UiO-67-(SH) Single Crystals. Into a 25 mL
Hz), 115.84 (s), 115.60 (s), 52.59 (s). FT-IR (KBr pellet, v/cm ):
2
Schlenk tube charged with H DMBPD (30 mg, 0.0979 mmol) was
1
1
716 (s), 1620 (s), 1558 (m), 1439 (s), 1396 (s), 1311 (s), 1288 (s),
254 (s), 1215 (m), 1192 (m), 1138 (s), 1107 (m), 1045 (w), 879
2
added N,N-diethylformamide (DEF, 1.1 mL) solution containing
ZrCl (22.8 mg, 0.0978 mmol) and benzoic acid (478 mg, 3.92
(
w), 852 (w), 775 (m), 690 (w).
4
mmol). The tube was inserted into liquid N to freeze the mixture and
Synthesis of Dimethyl 3,3′-Bis(benzylthio)biphenyl-p,p′-
2
dicarboxylate (SM2). Into a two-necked, round-bottomed flask
containing a magnetic stirring bar, SM1 (1.0 g, 3.26 mmol), and
K CO (3.16 g, 22.8 mmol) on a nitrogen manifold was cannulated
then evacuated in an oil pump vacuum. The tube was then screw-
capped, naturally warmed to rt, and then heated at 120 °C in an oven
for 24 h, followed by programmed cooling to rt over 12 h (at a rate of
2
3
−1
deaerated N-methyl-2-pyrrolidone (NMP, 27 mL; bubbled with N2
for 15 min), and stirring was started. Benzyl mercaptan (1.0 mL, 8.52
7.9 °C h ). The resulting light yellow crystals were washed with
DMF by decanting (5 × 3 mL) and then immersed in DMF for
storage. For weighing, the crystals were solvent-exchanged with
acetone (5 × 5 mL; over 10 min each time) and then dried in vacuo
(yield 23.6 mg).
mmol) was added under N protection, and the reaction mixture was
2
stirred at 50 °C for 2 days. After cooling to rt, methyl iodide (1.0 mL,
1
6 mmol) was injected under N protection and stirred for 1 h. The
2
resulting mixture was then poured into distilled water (300 mL); 15
min later, the solid thereof was collected by suction filtration, washed
with distilled water (3 × 100 mL), and dried in the air stream to
Bulk Synthesis of Polycrystalline UiO-67-(SH)
a 10 mL glass ampule charged with H DMBPD (120 mg, 0.39 mmol)
was added a DEF (7.0 mL) solution containing ZrCl (91.2 mg, 0.390
2
Sample. Into
2
4
1
afford S7 as a white solid (1.64 g, 97.4% yield based on SM1). H
mmol) and benzoic acid (1.435 g, 11.75 mmol). The ampule was then
evacuated by in oil pump vacuum (with the content being frozen in
liquid nitrogen) and flame-sealed. The ampule was then naturally
warmed to rt, heated at 120 °C in an oven for 24 h, and program-
NMR (400 MHz, CDCl ) δ = 7.74−7.68 (m, 2H), 7.36 (d, J = 1.7
3
Hz, 2H), 7.31 (d, J = 7.2 Hz, 4H), 7.22 (t, J = 7.3 Hz, 4H), 7.19−7.13
1
3
(
m, 4H), 4.02 (s, 4H), 3.77 (s, 6H). C NMR (100 MHz, CDCl ) δ
3
−1
=
166.59 (s), 143.75 (s), 142.75 (s), 135.99 (s), 131.85 (s), 129.02
cooled back to rt over 12 h (at a rate of 7.9 °C h ). The solid
product was washed with DMF (5 × 5 mL) and then stored in DMF.
For weighing, the solid was solvent-exchanged with acetone (5 × 5
mL; over 10 min each time) and then dried in vacuo to give a light
(
(
(
s), 128.73 (s), 127.51 (s), 126.93 (s), 124.79 (s), 123.07 (s), 52.25
s), 37.29 (s). FT-IR (KBr pellet, v/cm ): 2951 (m), 1713 (s), 1589
m), 4868 (m), 1493 (m), 1470 (m), 1454 (m), 1439 (m), 1281 (s),
−
1
B
Inorg. Chem. XXXX, XXX, XXX−XXX