Supporting Information
A Tale of Copper Coordination Frameworks: Controlled SingleCrystal-to-Single-Crystal Transformations and Their Catalytic C H
Bond Activation Properties
Yifa Chen,[a] Xiao Feng,[a] Xianqiang Huang,[a, b] Zhengguo Lin,[a] Xiaokun Pei,[a] Siqing Li,[a]
Jikun Li,[a] Shan Wang,[a] Rui Li,[a] and Bo Wang*[a]
chem_201501672_sm_miscellaneous_information.pdf
Table of contents
1. Experimental procedures
2. Table S1. Crystallographic Data for 1D-MOF
3. Figure S1.The PXRD and structure of synthesized MOP-1
4. Figure S2. The PXRD and structure of synthesized 1D-MOF
5. Figure S3. The PXRD and structure of synthesized MOF-505
6. Figure S4.The PXRD and structure of synthesized Cu-pdc-MOF
7. Figure S5.The PXRD and structure of synthesized HKUST-1
8. Figure S6. The PXRD and structure of synthesized MOF-14
9. Figure S7.The SEM and optical microscope of HKUST-1
10. Figure S8. The PXRD of MOP-1 after catalysis
11. Figure S9. The PXRD of 1D-MOF after catalysis
12. Figure S10. The PXRD of HKUST-1 after catalysis
13. Table S2. The catalysis time and conversion of MOP-1, 1D-MOF, HKUST-1 and Cu(NO3)2·3H2O
14. Figure S11. The possible catalysis mechanism of MOP-1, 1D-MOF and HKUST-1
1. Experimental procedures
Materials:
Isophthalic acid (Sigma-Aldrich, 99%), Cu(NO3)2·3H2O (Sigma-Aldrich, 99%), Trimesic acid (Aladdin, 98%), 1,
3, 5-tris(4-carboxyphenyl) benzene (Sigma-Aldrich, 99%), 3,5-pyridinedicarboxylic acid (Chemsoon, 98%),
tetratopic biphenyl-3, 3’, 5, 5’-tetracarboxylic acid (Chemsoon, 99%) were all obtained from commercial sources
and used without further purification.
Instrumentation:
Field-emission scanning electron microscopy (FESEM, JEOL, S-4800) was applied to investigate the size and
morphology of the samples. The metal content of the compounds was measured by inductively coupled plasma
(ICP) on a JY-ULTIMA2 analyzer. The FT-IR spectra were recorded from KBr pellets in the range 4000-400 cm-1
on Nicolet 170 SXFT-IR spectrometer. The GC analyses were performed on Shimadzu GC-2014C with a FID
detector equipped with an Rtx-1701 Sil capillary column. The GC mass spectra were recorded on Agilent 7890A-
5975C at an ionization voltage of 1200 V. The C, H, N elemental analyses were conducted on Perkin-Elmer 240C
elemental analyzer. Powder X-ray diffraction (PXRD) patterns of the samples were analyzed with
monochromatized Cu-Kα (λ = 1.54178 Å) incident radiation by a Shimadzu XRD-6000 instrument operating at 40
kV voltage and 50 mA current.
Syntheses of crystals:
MOP-1:
Isophthalic acid (70 mg, 0.42 mmol), Cu(NO3)2·3H2O (95 mg, 0.39 mmol) were added into a mixed solution of
DMF/ethanol (3:1, 10 mL) in a capped 20 mL glass vial, sonicated to be mixed and then heated to 85 °C for 24 h
followed by slowly cooling to room temperature over 3 h. Yield: 52 mg (74% based on isophthalic acid).
HKUST-1 from MOP-1:
MOP-1 (18 mg) and BTC (150 mg, 0.71 mmol) were added into a mixture of DMF/ethanol/H2O (1:1:1, 3 mL) in a
10 ml Teflon vial with additive of 0.1 mL TEA solution (1 mL TEA mixed with 5mL DMF) and then left to react
at 130 ºC for 24 h. Yield: 10.0 mg (55% based on MOP-1).
MOF-14 from MOP-1:
MOP-1 (15 mg) and BTB (150 mg, 0.34 mmol) were added into a mixture of DMF/ethanol/H2O (1:1:1, 3 mL) in a
10 ml Teflon vial and then left to react at 130 ºC for 24 h. Yield: 13.0 mg (87% based on MOP-1).
1D-MOF from MOP-1:
MOP-1 (500 mg) was added into 1-methylimidazole (10 mL, 125.46 mmol) solution in a capped glass vial and left
to react at room temperature for 12 h. Yield: 450 mg (90% based on MOP-1). IR (cm-1): 3122 (m), 3043 (w), 2933
(w), 2358 (w), 2331 (w), 1908 (w), 1699 (w), 1612 (s), 1560 (s), 1536 (s), 1484 (w), 1378 (s), 1348 (s), 1281 (m),
1243 (m), 1108 (s), 1025 (w), 943 (w), 920 (w), 875 (m), 815 (m), 755 (s), 657 (s). Elements analysis
(calculated, %) data for 1D-MOF: C, 50.32 (50.42); N, 17.84 (17.65); H, 3.78 (4.62); Cu, 13.38 (13.44).
MOF-505 from 1D-MOF:
1D-MOF (20 mg) and BPTC (50 mg, 0.15 mmol) were added into DMF (8 mL) in a 20 mL Teflon vial and
swirled by hand to mix, then left to react at 130 oC for 24 h. Yield: 16.0 mg (80% based on 1D-MOF).
Cu-pdc-MOF from 1D-MOF:
1D-MOF (18 mg) and 3,5-Pyridinedicarboxylic acid (50 mg, 0.30 mmol) were added into DMF (3 mL) in a 10 mL
Teflon vial and swirled by hand to mix, then left to react at 130 oC for 24 h. Yield: 12.0 mg (67% based on 1D-
MOF).
General Procedure of Catalyzed Oxidation of Diphenylmethane Using MOP-1, 1D-MOF, HKUST-1 and
Cu(NO3)2·3H2O:
Diphenylmethane (0.125 mmol, 21.025 mg), 70% TBHP (0.312 mmol, 65.180 mg) were added to three Schlenk
Tubes, MOP-1(5.0 mg, 0.02 mmol), 1D-MOF (7.4 mg, 0.02 mmol), HKUST-1 (4.2 mg, 0.02 mmol) and
Cu(NO3)2·3H2O (4.8 mg, 0.02 mmol) were added for corresponding tubes. And then 0.5 mL of benzonitrile was
added to each tube. The reaction mixture was subsequently heated at 60 °C in a Wattecs Parallel Reactor for 24 h
with stirring. After the reaction was completed, products were analyzed by GC-MS and GC.
X-ray Crystallography:
Single-crystal X-ray diffraction data of 1D-MOF was collected on a Bruker-AXS CCD diffractometer equipped
with a graphite-monochromated Mo-Ka radiation (λ= 0.71073 Å) at 77 K. All absorption corrections were applied
using multi-scan technique. The structures were solved by the direct method and refined through full-matrix leastsquares techniques method on F2 using the SHELXTL 97 crystallographic software package. The hydrogen atoms
of the organic ligands were refined as rigid groups. Crystallographic Data for 1D-MOF is summarized in Table S1.
The crystallographic data have been deposited with the Cambridge Crystallographic Data Centre (CCDC) as entry
975073 for 1D-MOF.
Table S1. Crystallographic Data for 1D-MOF
Compounds
1D-MOF
Formula
C20H22N6O4Cu
Mr
473.98
Space group
P 21/n
Temperature
293(2) K
a (Å)
9.0198(18)
b (Å)
19.230(4)
c (Å)
12.410(3)
α (deg)
90
β (deg)
93.14(3)
γ (deg)
90
V
(Å3)
Z
Dcalc.(g
2149.29(7)
4
cm-3)
1.465
F(000)
980
R1[I>2σ(I)]
0.0330
wR2[I>2σ(I)]
0.0753
R1(all data)
0.0415
wR2(all data)
0.0790
GOOF
1.053
CCDC
975073
Figure S1. The PXRD pattern and crystal structure of MOP-1. Black, simulated MOP-1; red, as-synthesized MOP-1.
Figure S2. The PXRD pattern and crystal structure of 1D-MOF. Black: simulated 1D-MOF; red, as-synthesized 1D-MOF.
Figure S3. The PXRD pattern and crystal structure of MOF-505. Black: simulated MOF-505; red: as-synthesized MOF-505.
Figure S4. The PXRD pattern and crystal structure of Cu-pdc-MOF. Black: simulated Cu-pdc-MOF; red: as-synthesized Cu-pdcMOF.
Figure S5. The PXRD pattern and crystal structure of HKUST-1. Black: simulated HKUST-1; red: as-synthesized HKUST-1.
Figure S6. The PXRD pattern and crystal structure of MOF-14. Black: simulated MOF-14; red: as-synthesized MOF-14.
Figure S7. The SEM and optical microscope images of HKUST-1: a) and b) the SEM images of obtained HKUST-1; c) the
optical microscope image of HKUST-1 obtained from crystal transformation; d) the optical microscope image of HKUST-1
directly synthesized from Cu(NO3)2 and BTC. The scale bar represented here is 20 µm.
Figure S8. The PXRD of MOP-1 after catalysis. Black: simulated MOP-1; red: MOP-1 after catalysis.
Figure S9. The PXRD of 1D-MOF after catalysis. Black: simulated 1D-MOF; red: 1D-MOF after catalysis.
Figure S10. The PXRD of HKUST-1 after catalysis. Black: simulated HKUST-1; red: HKUST-1 after catalysis.
Table S2 The catalysis time and conversions of MOP-1, 1D-MOF, HKUST-1 and Cu(NO3)2·3H2O.
Catalyst
21 h
22 h
23 h
24h
MOP-1
86.2%
87.9%
91.8%
91.6%
1D-MOF
88.5%
91.6%
93.9%
94.3%
HKUST-1
80.1%
83.4%
85.1%
87.0%
Cu(NO3)2·
3H2O
48.8%
48.9%
48.9%
48.8%
The selectivity of MOP-1,1D-MOF and 3D-MOF after 24h was calculated to be 92.5%, 96.1% and 93.9%.
Figure S11. The possible catalysis mechanism of Copper based composites: MOP-1, 1D-MOF and HKUST-1