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Supporting Information © Wiley-VCH 2006
69451 Weinheim, Germany
S1
Polymer-Induced Heteronucleation for the Discovery of New Extended Solids
Adam L. Grzesiak, Fernando J. Uribe, Nathan W. Ockwig, Omar M. Yaghi, Adam J. Matzger
Vibrational Spectroscopy: Raman spectra were obtained using a Renishaw inVia Raman microscope equipped with a 785 nm diode laser and a 1200 lines/mm grating. Spectra were collected and analyzed using the WiRE 2.0 software package. Calibration was performed using a silicon standard. Spectra were typically collected in extended scan mode with a range of 100-3200 cm-1. FTIR spectra were recorded on a Perkin-Elmer Spectrum BX FTIR system. The scan range was 400–4000 cm-1, using eight scans per spectrum with a resolution of 1 cm-1. Spectra were obtained in the transmission mode in KBr pellets.
Figure 1. Raman spectrum of PNMOF-1 and MOF-5.
Table 1. Raman shifts for PNMOF-1 and MOF-5.
Raman Shift (cm-1) PNMOF-1 IRMOF-1 100-600 Three peaks at
284, 353, and 427 Three peaks at 277, 352, and 429
601-840 Four peaks at 635, 777, 817, and 826
Four peaks at 635, 774, 818, and 824
841-1025 Three peaks at 871, 945, and 994
Three peaks at 863, 945, and 995
1026-1200 Three peaks at 1085, 1138, and 1175
Three peaks at 1084, 1138, and 1171
1201-1520 Four peaks at 1212, 1265, 1430, and 1504
Five peaks at 1215, 1268, 1305, 1435, and 1503
1521-1700 Three peaks at 1552, 1613, and 1663
Three peaks at 1561, 1614, and 1660
2500-2700 Two peaks at 2596 and 2610
Two peaks at 2596 and 2610
2701-3200 Two peaks at 2879 and 2942
Two peaks at 2879 and 2940
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Figure 2. Raman spectrum of PNMOF-2 and IRMOF-2.
Table 2. Raman shifts for PNMOF-2 and IRMOF-2. Raman Shift (cm-1) PNMOF-2 IRMOF-2
100-600 Four peaks at 160, 298, 322, and 926
Six peaks at 159, 287, 320, 346, 426, and 494
601-840 Five peaks at 663, 737, 776, 805, and
826
Six peaks at 641, 662, 740, 773, 808, and 825
841-1025 Three peaks at 885, 944, and 997
Four peaks at 860, 889, 944, and 999
1026-1200 Five peaks at 1038, 1083, 1124,
1147, and 1160
Five peaks at 1040, 1084, 1110,
1129, and 1150 1201-1520 Three peaks at
1266, 1428, and 1457
Three peaks at 1265, 1428, and
1457 1521-1700 Three peaks at
1546, 1602, and 1662
Three peaks at 1540, 1603, and
1662 2701-3200 Two peaks at
2876 and 2939 Two peaks at
2877 and 2940
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400900140019002400290034003900
cm-1
%T
PNMOF-3
IRMOF-3
Figure 3. FTIR spectrum of PNMOF-3 and IRMOF-3.
Table 3. IR absorption peaks form NH2BDC MOFs. Wave Number
(cm-1) IRMOF-3 PNMOF-3
4000-3201 Two peaks at 3460 and 3356
Two peaks at 3464 and 3356
3200-2800 Three peaks at 2978, 2938, and
2878
Three peaks at 2980, 2940, and
2878 1800-1516 Two peaks at
1646 and 1578 Two peaks at
1640 and 1578 1515-1171 Five peaks at
1496, 1438, 1384, 1262, and 1214
Six peaks at 1496, 1422, 1384, 1298,
1262, and 1212 1170-871 Four peaks at
1106, 1026, 944, and 896
Five peaks at 1156, 1122, 1104,
1022, and 946 870-721 Three peaks at
828, 800, and 770 Three peaks at
828, 800, and 772 720-400 Six peaks at 698,
660, 646, 588, 516, and 442
Five peaks at 702, 662, 586, 524, and
438
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Figure 4. PXRD pattern for PNMOF-1 with peaks at 2θ = 8.73, 10.26, 10.52, 15.14, 17.04, 17.32, 17.83, 19.38, 19.76, 25.08, 27.05, 29.69, 30.53, 32.19, 33.04°.
Figure 5. PXRD pattern for PNMOF-2 with peaks at 2θ = 7.37, 8.89, 10.01, 11.49, 11.92, 17.54, 20.94, 21.99, 24.04, 27.25, 29.32°.
Figure 6. PXRD pattern for PNMOF-3 with peaks at 2θ = 5.93, 6.73, 7.13, 9.75, 14.79, 16.65, 19.45, 21.05, 24.36, 26.12, 31.50°.
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5% MAA 10% MAA 15% MAA
20% MAA 25% MAA 30% MAA
40% MAA 50% MAA 60% MAA
polydivinylbenzene polypropylene Figure 7. PNMOF-1 (plates) and MOF-5 (cubes) growing from MAA-DVB copolymers, polydivinylbenzene, and polypropylene.
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5% 4VP 10% 4VP 15% 4VP
20% 4VP 25% 4VP 30% 4VP
40% 4VP 50% 4VP 60% 4VP
70% 4VP Figure 8. PNMOF-1 (plates) and MOF-5 (cubes) growing from 4VP-DVB copolymers.
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5% 4VP 10% 4VP 15% 4VP
20% 4VP 25% 4VP 30% 4VP
40% 4VP 50% 4VP 60% 4VP
polydivinylbenzene polypropylene Figure 9. PNMOF-2 (plates) and IRMOF-2 (cubes) growing from 4VP-DVB copolymers, polydivinylbenzene, and polypropylene.
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5% MAA 10% MAA 15% MAA
20% MAA 25% MAA 30% MAA
40% MAA 50% MAA polydivinylbenzene
polypropylene Figure 10. PNMOF-3 (hexagonal faces) and IRMOF-3 (cubes) growing from MAA-DVB copolymers, polydivinylbenzene, and polypropylene.
S9
Figure 11. Metal-organic clusters of a) PNMOF-1, b) PNMOF-2, and c) PNMOF-3 representing the secondary building units (SBUs) and linear linkers. Hydrogen atoms have been removed for clarity and disordered atoms are shown in their highest occupancy positions.