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Thermally/hydrolytically Stable Covalent Organic Frameworks from a Rigid Macrocyclic Host Jing-Ru Song,a Junliang Sun,*b Junmin Liu,*c Zhi-Tang Huanga and Qi-Yu Zheng*a 5
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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x Two new 2D COFs were synthesized from triformylcyclotrianisylene, which show not only thermal stability but also hydrolytic stability. CTV-COF-1 with smaller pore size stored higher hydrogen of 1.3 wt% at low pressure, while CTV-COF-2 with larger pore size showed superior carbon dioxide uptake up to 250 cm3 g-1 at 298 K and 50 bar.
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Recently, porous materials have attracted tremendous interest due to their remarkable performance in the fields of gas storage, separation, heterogeneous catalysis and optoelectronics.1 Among of them, metal-organic frameworks (MOFs) show better controllability in the construction of desired frameworks/pores.2 However, the heavy metal ions made MOFs a little difficult to satisfy the established gravimetric gas storage targets for further energy application. Thus organic porous materials became the new candidates, which possess the high surface area and lower density due to the light component such as boron, nitrogen, silicon, oxygen and carbon. Although the synthesis of porous organic polymers3 is easy, the amorphous networks and corresponding wide pore size distribution limit their further application in some respect. The preeminent progress has been made in 2005 by Yaghi when the first covalent organic framework (COF) was constructed based on the reversible B-O formation.4 The COFs5 have similar porous properties to MOFs but lower density, and microcrystalline phase compared to porous organic polymers. Besides, COFs have controllable dimension and tailorable pore size from microporosity to mesoporosity by changing the building blocks. So far, various reversible covalent bonds including B-O, C-N and B-N have been used to build the frameworks,6-8 which showed excellent properties in many fields such as gas storage,9 photoelectric applications,10 and catalysis.11 However, it is not easy to construct a stable and functionalized COF rationally, which is mainly due to the property and limit of reversible covalent bonds. Weaker bonding can’t be dominant to direct the construction as desired, and also makes the organic framework much sensitive to the environment. On the other side, stronger bonding will hinder the self-correction when wrong networks are forming, which finally result in amorphous polymers. Cyclotriveratrylene (CTV) and its analogs are interesting pyramidal macrocycles with a shallow rigid cavity, which have been explored and used in molecular recognition and assembly.12 In previous research of porous materials, McKeown reported a polymer with intrinsic microporosity from cyclotricatechylene This journal is © The Royal Society of Chemistry [year]
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(CTC) building block, which showed better hydrogen uptake capacity.13 The first COF from CTC was synthesized by our group with reversible B-O bonds, which possessed superior hydrogen storage capacity than the similar planar motif.14 Though the excellent gas storage ability, COFs based on boronate are much sensitive to aqueous environment even humid air because of the weak B-O bond.15 Thus, it is necessary to find new method to increase the hydrolytic stability but maintain the outstanding gas storage capacity. Imine-linked 3D COF-300 had been synthesized by Yaghi, exhibiting highly ordered porous architecture.7a Imine bonds in polymer show less susceptive to moisture than boronate linkage. Combining the superior property of macromolecule with the well stability of imine-bond, here we synthesized two imine-linked covalent organic frameworks, CTV-COF-1 and CTV-COF-2. The COFs were synthesized by the condensation of triformylcyclotrianisylene (f-CTV) and aromatic amines under solvothermal conditions (Scheme 1). The yellow powders are insoluble in most organic solvents such as CHCl3, THF, MeOH,
Scheme 1 The synthetic route to CTV-COFs.
[journal], [year], [vol], 00–00 | 1
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DMF and acetone. Model compound (MC) was also prepared by condensation of f-CTV with aniline to help confirm the character of the two CTV-COFs. (see ESI) FTIR spectra of CTV-COFs show vibrational bands for imine at 1624 and 1200 cm-1 for CTV-COF-1, and 1620 and 1202 cm-1 for CTV-COF-2 respectively, while 1620 and 1199 cm-1 for model compound. The intensity for formyl group at 1684 cm-1 attenuated dramatically, suggesting that the condensation reaction happened smoothly. The solid state 13C CP-MAS NMR spectra further confirm the formation of the expected imine-bond. Thermogravimetric analysis (TGA) was done on the dry COFs under nitrogen atmosphere, which shows that they are stable up to 435 oC for CTV-COF-1 and 409 oC for CTV-COF-2. Scanning electron microscopy (SEM) exhibit only one morphologically unique crystalline phase, confirming the phase purity. (see ESI) The crystallinity of CTV-COFs was determined by powder Xray diffraction analysis. It displayed a main peak at 3.98o, with minor peaks at 6.92, 12.06, 16.34, 17.98 and 21.86 for CTVCOF-1 (Fig. 1); and 3.28, 5.68, 8.68, 13.20 for CTV-COF-2 (Fig. S12 in ESI). The reflections can be used to determine the hexagonal unit cell parameters as a = 25.76 Å and c = 4.90 Å for CTV-COF-1, and a = 30.76 Å, c = 4.90 Å for CTV-COF-2. To elucidate the lattice packing, we constructed crystal models with the space group of P-321 for eclipsed models and P63 for staggered models with doubled c-axes, respectively. A geometrical energy minimization was performed using the universal force-field to optimize the geometry of the building molecule with the unit cell fixed. From the simulated powder Xray diffraction patterns, we got excellent agreements with the experimental data according to the eclipsed model for both CTVCOF-1 and CTV-COF-2. On the basis of above experimental and calculated result, we conclude that the two COFs stack in the eclipsed arrangement, forming a 1D pore along c axis. (Fig. 2) The CTV skeletons packed in a columnar manner with the same chiral units, and thus avoid sliding between layers. The shortest interlayer C-C distances in the eclipsed models are about 3.6 Å and 3.5 Å for two COFs, showing weak π -π interactions. The hydrolytic stability test was examined by soaking CTVCOF-1 in water for 5, 10 and 48 h, and no color change was observed. These materials were then recovered by filtration, washed with acetone to remove the possible monomers, and then dried for 10 h in vacuum. The recovered materials were evaluated after hydrolysis using powder X-ray diffraction. As shown in Fig. S14, peak and the ratio of peaks intensity are all kept comparing with the original CTV-COF-1. The FTIR spectra further confirmed the retentivity of the structure. (see ESI) To investigate the architectural stability and porosity, nitrogen adsorption were investigated at 77 K. CTV-COF-1 exhibited a type-I isotherm showing a sharp uptake in low pressure (P/P0﹤ 0.10) demonstrating a permanent microporosity with little hysteresis upon desorption. The isotherm for CTV-COF-2 revealed a type-IV behaviour which exhibited a sharp adsorption for P/P0 from 0.02 to 0.15, indicating a narrow mesoporous distribution (Fig. S15). The BET surface areas for CTV-COF-1 and CTV-COF-2 were calculated to be 1245 and 1170 m2 g-1. The estimated total pore volumes are 0.9345 and 1.0665 cm3 g-1 for CTV-COF-1 and CTV-COF-2, respectively. Density functional theory (DFT) model was fitted to the isotherms resulting in pore
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Fig. 1 Comparison of the experimentally observed PXRD pattern (top) with the simulated eclipsed pattern (bottom) for CTV-COF-1.
Fig. 2 Stick view of CTV-COF-1. All hydrogen atoms are omitted for clarity. Different layers were shown as different colour. 65
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size of 1.48 nm and 2.16 nm for CTV-COF-1 and CTV-COF-2 respectively. These values fit the measured pore sizes (1.6 nm and 2.3 nm respectively) perfectly from the eclipsed structure models. Hydrogen adsorption was conducted at low pressure (0823mmHg) at 77 K, and the results were showed in Fig. 3. The maximum uptake from CTV-COF-1 was 1.3 wt% at 823 mmHg and 1.23 wt% at 760 mmHg, exceeding our CTC-COF (1.12 wt%, 1.05 bar), much close to 3D COF-103 (1.29 wt%, 1 bar).6d For CTV-COF-2, the maximum uptake is 0.75 wt% at 823 mmHg, which is due to the lower surface area and larger pore size than CTV-COF-1. Carbon dioxide excess uptake was also tested at 298 K and 50 bar (Fig. 4). Different from the hydrogen uptake, the maximum uptake for CO2 is CTV-COF-2, up to 250 cm3 g-1 (491 mg g-1), higher than COF-1, COF-6 and MOF-5 (230 mg g-1; 310 mg g-1, 55 bar; 420 mg g-1, 40 bar, total uptake).9a Both of the two COFs have large surface area, narrow pore width distribution and large pore volume, which is favourable to gas sorption. CTV-COF-1 has larger surface area and smaller pore width than CTV-COF-2, thus resulting in higher H2 uptake. The accessible nitrogen sites in the CTV-COFs can preferentially bind CO2 through the nitrogen lone-pair of –C=N– and the carbon atom of O=C=O which may distribute to the good CO2 uptake. In conclusion, two imine-linked CTV-COFs were firstly synthesized. The columnar manner from crown CTV motif
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Chemical Communications Accepted Manuscript
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Fig. 3 Hydrogen uptake (cycle: CTV-COF-1; triangle: CTV-COF-2). 4 55
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Fig. 4 Carbon dioxide excess uptake (filled simple for adsorption and open simple for desorption; cycle: CTV-COF-1; triangle: CTV-COF-2.
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avoids sliding between layers and well stabilizes the perfect eclipsed stack model than COFs based on planar motif in which the layers are not exactly eclipsed packed but slightly offset from one another. Compared to the boronate CTC-COF, the CTVCOFs show higher hydrolytic stability and exhibit moderate adsorption ability for carbon dioxide, and well hydrogen uptake which is comparable with 3D COFs. Financial support from the NSFC (20932004) and MOST of China (2011CB932501, 2013CB834504).
Notes and references
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Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China. Fax: (+86) 10 6255 4449; Tel: (+86) 010 6265 2811; E-mail: [email protected] b Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China E-mail: [email protected] c Klghei of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China. E-mail: [email protected] † Electronic Supplementary Information (ESI) available: Experimental details, FTIR spectra, 13C CP-MAS NMR spectra, thermogravimetric analysis, scanning electron microscopy, PXPD spectra, BET plot and pore size distribution, model of CTV-COFs, CD spectra and fractional atomic coordinates for the COFs. See DOI: 10.1039/b000000x/ 1 (a) T. A. Makal, J.-R. Li, W. Lu and H.-C. Zhou, Chem. Soc. Rev., 2012, 47, 7761; (b) N. B. McKeown and P. M. Budd, Chem. Soc. Rev., 2006, 35, 675; (c) Y. Zhang and S. N. Riduan, Chem. Soc. Rev., 2012, 41, 2083; (d) Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev.,
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Chemical Communications Accepted Manuscript
DOI: 10.1039/C3CC47652A
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Accepted Manuscript This article can be cited before page numbers have been issued, to do this please use: J. Song, J. L. Sun, J. Liu, Z. Huang and Q. Zheng, Chem. Commun., 2013, DOI: 10.1039/C3CC47652A.
Volume 46 | Number 32 | 2010
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This is an Accepted Manuscript, which has been through the RSC Publishing peer review process and has been accepted for publication. Chemical Communications www.rsc.org/chemcomm
Volume 46 | Number 32 | 28 August 2010 | Pages 5813–5976
ChemComm
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to therapeutic
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Accepted Manuscripts are published online shortly after acceptance, which is prior to technical editing, formatting and proof reading. This free service from RSC Publishing allows authors to make their results available to the community, in citable form, before publication of the edited article. This Accepted Manuscript will be replaced by the edited and formatted Advance Article as soon as this is available. To cite this manuscript please use its permanent Digital Object Identifier (DOI®), which is identical for all formats of publication.
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Pages 5813–5976
org/journals
ISSN 1359-7345
COMMUNICATION J. Fraser Stoddart et al. Directed self-assembly of a ring-in-ring complex
FEATURE ARTICLE Wenbin Lin et al. Hybrid nanomaterials for biomedical applications
1359-7345(2010)46:32;1-H
Please note that technical editing may introduce minor changes to the text and/or graphics contained in the manuscript submitted by the author(s) which may alter content, and that the standard Terms & Conditions and the ethical guidelines that apply to the journal are still applicable. In no event shall the RSC be held responsible for any errors or omissions in these Accepted Manuscript manuscripts or any consequences arising from the use of any information contained in them.
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DOI: 10.1039/C3CC47652A
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COMMUNICATION
Thermally/hydrolytically Stable Covalent Organic Frameworks from a Rigid Macrocyclic Host Jing-Ru Song,a Junliang Sun,*b Junmin Liu,*c Zhi-Tang Huanga and Qi-Yu Zheng*a 5
10
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x Two new 2D COFs were synthesized from triformylcyclotrianisylene, which show not only thermal stability but also hydrolytic stability. CTV-COF-1 with smaller pore size stored higher hydrogen of 1.3 wt% at low pressure, while CTV-COF-2 with larger pore size showed superior carbon dioxide uptake up to 250 cm3 g-1 at 298 K and 50 bar.
50
55
15
20
25
30
35
40
45
Recently, porous materials have attracted tremendous interest due to their remarkable performance in the fields of gas storage, separation, heterogeneous catalysis and optoelectronics.1 Among of them, metal-organic frameworks (MOFs) show better controllability in the construction of desired frameworks/pores.2 However, the heavy metal ions made MOFs a little difficult to satisfy the established gravimetric gas storage targets for further energy application. Thus organic porous materials became the new candidates, which possess the high surface area and lower density due to the light component such as boron, nitrogen, silicon, oxygen and carbon. Although the synthesis of porous organic polymers3 is easy, the amorphous networks and corresponding wide pore size distribution limit their further application in some respect. The preeminent progress has been made in 2005 by Yaghi when the first covalent organic framework (COF) was constructed based on the reversible B-O formation.4 The COFs5 have similar porous properties to MOFs but lower density, and microcrystalline phase compared to porous organic polymers. Besides, COFs have controllable dimension and tailorable pore size from microporosity to mesoporosity by changing the building blocks. So far, various reversible covalent bonds including B-O, C-N and B-N have been used to build the frameworks,6-8 which showed excellent properties in many fields such as gas storage,9 photoelectric applications,10 and catalysis.11 However, it is not easy to construct a stable and functionalized COF rationally, which is mainly due to the property and limit of reversible covalent bonds. Weaker bonding can’t be dominant to direct the construction as desired, and also makes the organic framework much sensitive to the environment. On the other side, stronger bonding will hinder the self-correction when wrong networks are forming, which finally result in amorphous polymers. Cyclotriveratrylene (CTV) and its analogs are interesting pyramidal macrocycles with a shallow rigid cavity, which have been explored and used in molecular recognition and assembly.12 In previous research of porous materials, McKeown reported a polymer with intrinsic microporosity from cyclotricatechylene This journal is © The Royal Society of Chemistry [year]
60
65
(CTC) building block, which showed better hydrogen uptake capacity.13 The first COF from CTC was synthesized by our group with reversible B-O bonds, which possessed superior hydrogen storage capacity than the similar planar motif.14 Though the excellent gas storage ability, COFs based on boronate are much sensitive to aqueous environment even humid air because of the weak B-O bond.15 Thus, it is necessary to find new method to increase the hydrolytic stability but maintain the outstanding gas storage capacity. Imine-linked 3D COF-300 had been synthesized by Yaghi, exhibiting highly ordered porous architecture.7a Imine bonds in polymer show less susceptive to moisture than boronate linkage. Combining the superior property of macromolecule with the well stability of imine-bond, here we synthesized two imine-linked covalent organic frameworks, CTV-COF-1 and CTV-COF-2. The COFs were synthesized by the condensation of triformylcyclotrianisylene (f-CTV) and aromatic amines under solvothermal conditions (Scheme 1). The yellow powders are insoluble in most organic solvents such as CHCl3, THF, MeOH,
Scheme 1 The synthetic route to CTV-COFs.
[journal], [year], [vol], 00–00 | 1
Chemical Communications Accepted Manuscript
Published on 24 October 2013. Downloaded by Lomonosov Moscow State University on 30/10/2013 16:11:53.
www.rsc.org/xxxxxx
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DMF and acetone. Model compound (MC) was also prepared by condensation of f-CTV with aniline to help confirm the character of the two CTV-COFs. (see ESI) FTIR spectra of CTV-COFs show vibrational bands for imine at 1624 and 1200 cm-1 for CTV-COF-1, and 1620 and 1202 cm-1 for CTV-COF-2 respectively, while 1620 and 1199 cm-1 for model compound. The intensity for formyl group at 1684 cm-1 attenuated dramatically, suggesting that the condensation reaction happened smoothly. The solid state 13C CP-MAS NMR spectra further confirm the formation of the expected imine-bond. Thermogravimetric analysis (TGA) was done on the dry COFs under nitrogen atmosphere, which shows that they are stable up to 435 oC for CTV-COF-1 and 409 oC for CTV-COF-2. Scanning electron microscopy (SEM) exhibit only one morphologically unique crystalline phase, confirming the phase purity. (see ESI) The crystallinity of CTV-COFs was determined by powder Xray diffraction analysis. It displayed a main peak at 3.98o, with minor peaks at 6.92, 12.06, 16.34, 17.98 and 21.86 for CTVCOF-1 (Fig. 1); and 3.28, 5.68, 8.68, 13.20 for CTV-COF-2 (Fig. S12 in ESI). The reflections can be used to determine the hexagonal unit cell parameters as a = 25.76 Å and c = 4.90 Å for CTV-COF-1, and a = 30.76 Å, c = 4.90 Å for CTV-COF-2. To elucidate the lattice packing, we constructed crystal models with the space group of P-321 for eclipsed models and P63 for staggered models with doubled c-axes, respectively. A geometrical energy minimization was performed using the universal force-field to optimize the geometry of the building molecule with the unit cell fixed. From the simulated powder Xray diffraction patterns, we got excellent agreements with the experimental data according to the eclipsed model for both CTVCOF-1 and CTV-COF-2. On the basis of above experimental and calculated result, we conclude that the two COFs stack in the eclipsed arrangement, forming a 1D pore along c axis. (Fig. 2) The CTV skeletons packed in a columnar manner with the same chiral units, and thus avoid sliding between layers. The shortest interlayer C-C distances in the eclipsed models are about 3.6 Å and 3.5 Å for two COFs, showing weak π -π interactions. The hydrolytic stability test was examined by soaking CTVCOF-1 in water for 5, 10 and 48 h, and no color change was observed. These materials were then recovered by filtration, washed with acetone to remove the possible monomers, and then dried for 10 h in vacuum. The recovered materials were evaluated after hydrolysis using powder X-ray diffraction. As shown in Fig. S14, peak and the ratio of peaks intensity are all kept comparing with the original CTV-COF-1. The FTIR spectra further confirmed the retentivity of the structure. (see ESI) To investigate the architectural stability and porosity, nitrogen adsorption were investigated at 77 K. CTV-COF-1 exhibited a type-I isotherm showing a sharp uptake in low pressure (P/P0﹤ 0.10) demonstrating a permanent microporosity with little hysteresis upon desorption. The isotherm for CTV-COF-2 revealed a type-IV behaviour which exhibited a sharp adsorption for P/P0 from 0.02 to 0.15, indicating a narrow mesoporous distribution (Fig. S15). The BET surface areas for CTV-COF-1 and CTV-COF-2 were calculated to be 1245 and 1170 m2 g-1. The estimated total pore volumes are 0.9345 and 1.0665 cm3 g-1 for CTV-COF-1 and CTV-COF-2, respectively. Density functional theory (DFT) model was fitted to the isotherms resulting in pore
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Fig. 1 Comparison of the experimentally observed PXRD pattern (top) with the simulated eclipsed pattern (bottom) for CTV-COF-1.
Fig. 2 Stick view of CTV-COF-1. All hydrogen atoms are omitted for clarity. Different layers were shown as different colour. 65
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size of 1.48 nm and 2.16 nm for CTV-COF-1 and CTV-COF-2 respectively. These values fit the measured pore sizes (1.6 nm and 2.3 nm respectively) perfectly from the eclipsed structure models. Hydrogen adsorption was conducted at low pressure (0823mmHg) at 77 K, and the results were showed in Fig. 3. The maximum uptake from CTV-COF-1 was 1.3 wt% at 823 mmHg and 1.23 wt% at 760 mmHg, exceeding our CTC-COF (1.12 wt%, 1.05 bar), much close to 3D COF-103 (1.29 wt%, 1 bar).6d For CTV-COF-2, the maximum uptake is 0.75 wt% at 823 mmHg, which is due to the lower surface area and larger pore size than CTV-COF-1. Carbon dioxide excess uptake was also tested at 298 K and 50 bar (Fig. 4). Different from the hydrogen uptake, the maximum uptake for CO2 is CTV-COF-2, up to 250 cm3 g-1 (491 mg g-1), higher than COF-1, COF-6 and MOF-5 (230 mg g-1; 310 mg g-1, 55 bar; 420 mg g-1, 40 bar, total uptake).9a Both of the two COFs have large surface area, narrow pore width distribution and large pore volume, which is favourable to gas sorption. CTV-COF-1 has larger surface area and smaller pore width than CTV-COF-2, thus resulting in higher H2 uptake. The accessible nitrogen sites in the CTV-COFs can preferentially bind CO2 through the nitrogen lone-pair of –C=N– and the carbon atom of O=C=O which may distribute to the good CO2 uptake. In conclusion, two imine-linked CTV-COFs were firstly synthesized. The columnar manner from crown CTV motif
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Fig. 3 Hydrogen uptake (cycle: CTV-COF-1; triangle: CTV-COF-2). 4 55
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Fig. 4 Carbon dioxide excess uptake (filled simple for adsorption and open simple for desorption; cycle: CTV-COF-1; triangle: CTV-COF-2.
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avoids sliding between layers and well stabilizes the perfect eclipsed stack model than COFs based on planar motif in which the layers are not exactly eclipsed packed but slightly offset from one another. Compared to the boronate CTC-COF, the CTVCOFs show higher hydrolytic stability and exhibit moderate adsorption ability for carbon dioxide, and well hydrogen uptake which is comparable with 3D COFs. Financial support from the NSFC (20932004) and MOST of China (2011CB932501, 2013CB834504).
Notes and references
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Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China. Fax: (+86) 10 6255 4449; Tel: (+86) 010 6265 2811; E-mail: [email protected] b Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China E-mail: [email protected] c Klghei of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China. E-mail: [email protected] † Electronic Supplementary Information (ESI) available: Experimental details, FTIR spectra, 13C CP-MAS NMR spectra, thermogravimetric analysis, scanning electron microscopy, PXPD spectra, BET plot and pore size distribution, model of CTV-COFs, CD spectra and fractional atomic coordinates for the COFs. See DOI: 10.1039/b000000x/ 1 (a) T. A. Makal, J.-R. Li, W. Lu and H.-C. Zhou, Chem. Soc. Rev., 2012, 47, 7761; (b) N. B. McKeown and P. M. Budd, Chem. Soc. Rev., 2006, 35, 675; (c) Y. Zhang and S. N. Riduan, Chem. Soc. Rev., 2012, 41, 2083; (d) Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev.,
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DOI: 10.1039/C3CC47652A
