Kerneghan et al.
581
from Sigma-Aldrich and recrystallized from water prior to use.
IR spectra were recorded as KBr disks using a PerkinElmer
Spectrum BX FT-IR spectrometer.
filtration and washed with THF to give 3 (109 mg) as a beige
solid.
Samples for 13C CP-MAS NMR spectroscopy were ground
into fine powders and packed into 4 mm o.d. zirconia rotors.
NMR spectra were acquired with high-power proton decou-
Supplementary data
Supplementary data (synthesis and characterization, details
of spectroscopic characterization, powder X-ray diffraction
studies, characterization of model compounds, and represen-
tative thermogravimetric analysis) are available with the ar-
ticle through the journal Web site (www.nrcresearchpress.
com/cjc).
13
pling at 9.4 T (n ( C) = 100.6 MHz) using a Bruker Avance
0
III console and a 4 mm triple-resonance Bruker MAS NMR
probe. The magic angle was set by maximizing the number
7
9
of rotational echoes in a Br MAS NMR experiment on
powdered KBr. Carbon-13 CP-MAS NMR pulse calibrations
and chemical shift referencing were performed using adaman-
tane (d = 38.55 ppm for the high-frequency peak, relative to
Acknowledgments
1
the primary standard TMS). Ninety degree H pulse widths
We are grateful to the Natural Sciences and Engineering
Research Council of Canada (NSERC), the Canada Founda-
tion for Innovation, the Ontario Research Fund, and Wilfrid
Laurier University, Waterloo, Ontario, for financial support.
We are also grateful to Dr. T. Maris for powder X-ray diffrac-
tion studies and to Drs. S. Lang and J. Ripmeester for assis-
tance with the gas adsorption studies.
were 3.45 µs, contact pulses were 1.5 or 2.0 ms, acquisition
times were 40–50 ms, and recycle delays were 20–50 s. Ap-
proximately 1000 to 2000 scans were averaged for each of
the COF samples. MAS rates were chosen to eliminate the
overlap of spinning sidebands with resonances of interest,
and ranged from 11 111 to 13 600 Hz. FIDs were processed
with zero-filling, 15–20 Hz exponential apodization, and
Fourier transformation.
References
Gas adsorption isotherms were measured volumetrically
using a Micromeritics ASAP 2010 automated adsorption ana-
lyzer. Samples were degassed at room temperature for 7 h
prior to measurement. A liquid nitrogen bath (77 K) was
used for the N isotherms. The N gas used was UHP grade.
(
1) (a) Davis, M. E. Nature 2002 417 (6891), 813. doi:10.1038/
nature00785; (b) Morris, R. E.; Wheatley, P. S. Angew. Chem.
Int. Ed. 2008 47 (27), 4966. doi:10.1002/anie.200703934.
(2) For a recent review, see Long, J. R.; Yaghi, O. M. Chem. Soc.
Rev. 2009 38 (5), 1213. doi:10.1039/b903811f.
(3) For a recent review, see Maly, K. E. J. Mater. Chem. 2009 19
(13), 1781. doi:10.1039/b816089a.
2
2
Brunauer–Emmett–Teller (BET) method was used to deter-
2
–1
mine the specific surface areas (ABET, m g ) using the ad-
(
4) (a) Germain, J.; Hradil, J.; Fréchet, J. M. J.; Svec, F. Chem.
Mater. 2006 18 (18), 4430. doi:10.1021/cm061186p; (b)
Germain, J.; Fréchet, J. M. J.; Svec, F. J. Mater. Chem. 2007
sorption data over 0.05–0.20 relative pressure (P/P0).
Synthesis of network 17d
A pyrex glass tube with a 6 mm i.d. and an 8 mm o.d. was
charged with tetrakis(4-aminophenyl)methane (20 mg,
1
7 (47), 4989. doi:10.1039/b711509a.
5) (a) McKeown, N. B.; Budd, P. M. Chem. Soc. Rev. 2006 35
8), 675. doi:10.1039/b600349d; (b) Budd, P. M.; Butler, A.;
(
(
0
.052 mmol), terephthaldehyde (12 mg, 0.089 mmol), and a
Selbie, J.; Mahmood, K.; McKeown, N. B.; Ghanem, B.;
Msayib, K.; Book, D.; Walton, A. Phys. Chem. Chem. Phys.
mixture of dioxane (0.8 mL) and 2 mol/L AcOH (0.2 mL).
The tube was flash-frozen in liquid nitrogen, evacuated to a
pressure of 150 mTorr (1 Torr = 133.322 Pa), and flame-
sealed at a length of 12 cm. The contents of the tube were
allowed to warm to room temperature and then heated at
2
007 9 (15), 1802. doi:10.1039/b618053a; (c) Ghanem, B. S.;
Msayib, K. J.; McKeown, N. B.; Harris, K. D. M.; Pan, Z.;
Budd, P. M.; Butler, A.; Selbie, J.; Book, D.; Walton, A. Chem.
Commun. (Camb.) 2007 (1): 67. doi:10.1039/b614214a; (d)
Ghanem, B. S.; McKeown, N. B.; Budd, P. M.; Fritsch, D.
Macromolecules 2008 41 (5), 1640. doi:10.1021/ma071846r.
100 °C for 72 h. The yellow solid formed was collected via
filtration and washed repeatedly with THF. The yellow pre-
cipitate was collected and dried under vacuum at 100 °C for
(6) (a) Weber, J.; Antonietti, M.; Thomas, A. Macromolecules
2007 40 (4), 1299. doi:10.1021/ma062598m; (b) Thomas, A.;
Goettmann, F.; Antonietti, M. Chem. Mater. 2008 20 (3), 738.
doi:10.1021/cm702126j; (c) Weber, J.; Antonietti, M.;
Thomas, A. Macromolecules 2008 41 (8), 2880. doi:10.
2
4 h to evacuate the pores of all solvent guest molecules.
Yield: 48 mg.
Synthesis of network 2
1
021/ma702495r; (d) Jiang, J. X.; Su, F.; Trewin, A.; Wood,
An oven-dried flask was charged with 1 (104 mg) and
C. D.; Campbell, N. L.; Niu, H.; Dickinson, C.; Ganin, A. Y.;
Rosseinsky, M. J.; Khimyak, Y. Z.; Cooper, A. I. Angew.
Chem. Int. Ed. 2007 46 (45), 8574. doi:10.1002/anie.
purged with N (g) for 15 min. Borane–THF (15 mL, 1 mol/L)
2
was then added to the flask and the mixture was allowed to
stir for 24 h at room temperature. The solid was collected by
filtration and washed with THF to yield 97 mg of 2 as a
beige solid.
2
00701595; (e) Jiang, J.-X.; Su, F.; Trewin, A.; Wood, C.
D.; Niu, H.; Jones, J. T. A.; Khimyak, Y. Z.; Cooper, A. I. J.
Am. Chem. Soc. 2008 130 (24), 7710. doi:10.1021/ja8010176;
(
f) Farha, O. K.; Spokoyny, A. M.; Hauser, B. G.; Bae, Y.-S.;
Synthesis of network 3
Brown, S. E.; Snurr, R. Q.; Mirkin, C. A.; Hupp, J. T. Chem.
Mater. 2009 21 (14), 3033. doi:10.1021/cm901280w.
Network 2 (96 mg) was submerged in Ac O for 18 h to
2
allow Ac O to exchange into the pores of the network. This
2
(7) (a) Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.;
Matzger, A. J.; Yaghi, O. M. Science 2005 310 (5751), 1166.
doi:10.1126/science.1120411; (b) Côté, A. P.; El-Kaderi, H.
M.; Furukawa, H.; Hunt, J. R.; Yaghi, O. M. J. Am. Chem. Soc.
2007 129 (43), 12914. doi:10.1021/ja0751781; (c) El-Kaderi,
mixture was then placed into a sealed glass tube, heated to
1
00 °C, and stirred for 24 h. The solid was collected via fil-
tration, washed with THF, and submerged in THF for 24 h to
remove any remaining Ac O. The solid was collected via
2
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