preparation of a series of actv-based covalent organic ...4 0 0 0 3 0 0 0 2 0 0 0 1 0 0 0 2 0 4 0 6...
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Preparation of a series of aCTV-based covalent organic frameworks
and the substituent effect on their properties
Jingru Zhen,a Sanyuan Ding,b Junmin Liu,c Zhitang Huang,a Wei Wang,*b and Qiyu Zheng*a
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognitionand Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.b State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou, Gansu, 730000, China.c Klghei of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, SunYat-Sen University, Guangzhou, 510275, China.
Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2016
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Experimental section
O
O
OO
H3C
CH3
O
O
Br
H3C
CH3
Br+ N
O
+ BBr3
OH
OH
OO
1 2 3
2,5-dimethoxyterephthalaldehyde: n-Butyllithium (2.5 M in hexane) (8.8 ml, 22 mmol) was added to a solution of 2,5-dimethoxyterephthalaldehyde (1) (2.96 g, 10 mmol) in dry THF (50 ml) at -78 °C under an argon atmosphere. The solution was stirred for 3h at -78 °C . DMF (3.0 ml) was added to the mixture and the solution was stirred for 1h, and then was allowed to warm to room temperature for another 1h. Saturated ammonium chloride was added to the mixture to quench the reaction. THF was removed under reduced pressure. The organic layer was separated and the aqueous layer was extracted with 3 × 15 ml dichloromethane. The extract was dried over Na2SO4, and recrystallized from petrol ether. H-NMR (400 MHz; CDCl3): δ=10.5 (s, 2H), 7.5 (s, 2H), 4.0 (s, 6H); 13C NMR (400MHz; CDCl3) 189.6, 156.0, 129.4, 111.1, 56.3; m/z (ESI) 195(100%, M+).
2,5-dihydroxyterephthalaldehyde: 2,5-dimethoxyterephthalaldehyde (194 mg, 1 mmol) was dissolved in 10 ml DCM at 0 C under an argon atmosphere. 0.5 ml of BBr3 was added dropwise and stirred at room temperature for 4 hours. After complete reaction, the reacted mixture was neutralized with 10 ml H2O and stirred overnight, followed by extraction with water and DCM and recrystallization within DCM and PE to obtain 2, 5-dihydroxyterephthalaldehyde in 70% yield. H-NMR (400 MHz, DMSO): δ=10.30 (s, 2H), 7.20 (s, 2H; aromatic); m/z (ESI) 165 (100%, M+).
FTIR spectra:
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4000 3000 2000 1000
20
40
60
80
100
aCOF4
aCOF3
aCOF2
wavenumber (cm-1)
1698
1620
1698
1622
16811615
16601614
aCOF1
Fig. S1 FT-IR spectra of aCTV-COF1 (black), aCTV-COF2 (red), aCTV-COF3 (blue) and aCTV-COF4 (green)
4000 3000 2000 1000
0
50
100
wavenumber (cm-1)
16971620
16981622
16801614
1660
1613
Fig. S2 FT-IR spectra of aCTV-COF1 (black), aCTV-COF2 (red), aCTV-COF3 (blue) and aCTV-COF4 (green) in water for 10h
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4000 3000 2000 1000
aCOF4
aCOF3
aCOF2
Wavenumber (cm-1)
aCOF1
16981621
16981621
16801615
16621613
Fig. S3 FT-IR spectra of aCTV-COF1 (black), aCTV-COF2 (red), aCTV-COF3 (blue) and aCTV-COF4 (green) in water for 24h
13C CP-MAS NMR spectra for aCTV-COFs
Fig. S4 13C CP-MAS NMR spectra for aCTV-COF1
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Fig. S5 13C CP-MAS NMR spectra for aCTV-COF2
Fig. S6 13C CP-MAS NMR spectra for aCTV-COF3
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Fig. S7 13C CP-MAS NMR spectra for aCTV-COF4
TGA measurement for aCTV-COFs:
0 100 200 300 400 500 600 7000
20
40
60
80
100
weig
ht(%
)
Temprature(oC)
aCTV-COF-4 aCTV-COF-1 aCTV-COF-2 aCTV-COF-3
Fig. S8 TGA measurement for aCTV-COF-1 (red), aCTV-COF-2 (blue), aCTV-COF-3 (green) and aCTV-COF-4 (black).
PXRD
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Fig. S9 Comparison of the experimentally observed PXRD pattern with the simulated staggered pattern for aCTV-COFs
Fig. S10 Pore size distribution of aCTV-COFs
Models of CTV-COFs
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Fig. S11 Top view (a) and side view (b) of eclipsed aCTV-COF-1. C gray, O red, N blue, H white.
Fig. S12 Top view (a) and side view (b) of eclipsed aCTV-COF-2. C gray, O red, N blue, H white.
Fig. S13 Top view (a) and side view (b) of eclipsed aCTV-COF-3. C gray, O red, N blue, H white.
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Fig. S14Top view (a) and side view (b) of eclipsed aCTV-COF-4. C gray, O red, N blue, H white.
Fig. S15 Top view staggered aCTV-COF-1. C gray, O red, N blue, H white. Another layer is colored in orange.
Fig. S16 Top view staggered aCTV-COF-2. C gray, O red, N blue, H white. Another layer is colored in orange.
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Fig. S17 Top view staggered aCTV-COF-3. C gray, O red, N blue, H white. Another layer is colored in orange.
Fig. S18 Top view staggered aCTV-COF-4. C gray, O red, N blue, H white. Another layer is colored in orange.