Supplementary Materials for - Science · 2018. 7. 3. · Single-crystal x-ray Diffraction Analysis Section S4. Powder x-ray Diffraction Analysis Section S5. Solid-state Nuclear Magnetic

$Page 1: Supplementary Materials for - Science · 2018. 7. 3. · Single-crystal x-ray Diffraction Analysis Section S4. Powder x-ray Diffraction Analysis Section S5. Solid-state Nuclear Magnetic$
www.sciencemag.org/content/361/6397/48/suppl/DC1

Supplementary Materials for

Single-crystal x-ray diffraction structures of covalent organic frameworks

Tianqiong Ma*, Eugene A. Kapustin*, Shawn X. Yin, Lin Liang, Zhengyang Zhou, Jing Niu, Li-Hua Li, Yingying Wang, Jie Su, Jian Li, Xiaoge Wang, Wei David Wang, Wei Wang†,

Junliang Sun†, Omar M. Yaghi†

*These authors contributed equally to this work. †Corresponding author. Email: [email protected] (W.W.); [email protected] (J.S.)

[email protected] (O.M.Y.)

Published 6 July 2018, Science 361, 48 (2018) DOI: 10.1126/science.aat7679

This PDF file includes:

Materials and Methods Supplementary Text Figs. S1 to S35 Tables S1 to S7 References

Other Supplementary Materials for this manuscript include the following: (available at www.sciencemag.org/content/361/6397/48/suppl/DC1)

Crystal data and details of the structure refinement for single-crystal COFs:

Data file S1. CIF file for COF-300 Checkcif report for COF-300 (PDF) Data file S2. CIF file for COF-300_disorder Checkcif report for COF-300_disorder (PDF) Data file S3. CIF file for hydrated COF-300 Checkcif report for hydrated COF-300 (PDF) Data file S4. CIF file for LZU-79 Checkcif report for LZU-79 (PDF) Data file S5. CIF file for LZU-111 Checkcif report for LZU-111 (PDF)

2

Materials and Methods

Table of contents.

Section S1. Materials and Instrumentation

Section S2. Synthesis of COF Building Blocks and COF Crystallization

Section S3. Single-crystal x-ray Diffraction Analysis

Section S4. Powder x-ray Diffraction Analysis

Section S5. Solid-state Nuclear Magnetic Resonance Spectroscopic Analysis

Section S6. Fourier Transform Infrared Spectroscopic Analysis

Section S7. Thermogravimetric Analysis

Section S8. N2 Adsorption-desorption Analysis

Section S9. Scanning Electron Microscopy Images

3

Section S1. Materials and Instrumentation

Materials

(4-formylphenyl)boronic acid (purity ≥ 98%) and 2,3-dimethylbutane-2,3-diol (purity ≥

98%) were purchased from Energy Chemical Co. 4,7-dibromo-1H-benzo[d]imidazole

(purity ≥ 98%) was purchased from Zhengzhou Alfachem Co. Pd(PPh3)4 (purity ≥ 99%,

Pd 9%) was purchased from Beijing Innochem Science & Technology Co. K2CO3 (purity

≥ 99.0%) was purchased from Tianjin Kemiou Chemical Reagent Co. Anhydrous Na2SO4

(purity ≥ 99.0%) was purchased from Xilong Scientific Co. Aniline (AR, ≥ 99.5%) was

purchased from Chengdu Chron Chemicals Co. Diethyl ether (AR, ≥ 99.5%), ethyl

acetate (AR, ≥ 99.5%), 1,4-dioxane (AR, ≥ 99.5%), tetrahydrofuran (AR, ≥ 99.0%), and

glacial acetic acid (AR, ≥ 99.5%) were purchased from Tianjin Guangfu Fine Chemical

Research Institution. Isopropanol (AR, ≥ 99.7%) was purchased from Tianjin Fuyu Fine

Chemical Co. Cyclohexanol (AR, ≥ 99.0%) was purchased from Tianjin Fengyue

Chemical Co. All regents and solvents were used without further purification unless

otherwise specified.

Instrumentation

Single-crystal x-ray diffraction (SXRD). The laboratory SXRD data were collected at

150 K on an Agilent SuperNova diffractometer with a 4-circle kappa goniometer, an Eos

CCD detector, and a micro-focus high-brilliance source with Cu Κα radiation (λ = 1.5418

Å), and collected at 100 K on a Rigaku XtaLAB Rapid-S X-ray diffractometer with a 4-

circle kappa goniometer, an IP detector, and a rotating-anode generator producing Mo Κα

radiation (λ = 0.7107 Å). Data reduction and analysis were both performed with the

CrysAlisPro software (version 1.171.39.9f). The synchrotron SXRD data were collected

at the Beamline BL17B1, BL17U1 of Shanghai Synchrotron Radiation Facility (SSRF)

with λ = 0.9840 and 0.9786 Å; and at Beamline 11.3.1 of Advanced Light Source (ALS,

LBNL) with λ = 1.0332 and 1.2399 Å. All the datasets of single-crystal COFs were

collected at 100 K, and the data were accordingly processed with CrysAlisPro (version

1.171.37.35), HKL2000 (28), and APEXII (29) software packages, depending on the

instrument setup. The structure solution and refinement were carried out using the

SHELX algorithms in Olex2 (30, 31). Crystal data and details of the structure refinement

for single-crystal COFs are given in Tables S1-S7 and in the attached CIFs. Mercury and

Diamond softwares were used for structural visualization (32, 33).

Powder x-ray diffraction (PXRD). The PXRD data were collected on a PANalytical

X’Pert Pro diffractometer with Cu Kα radiation of λ = 1.5418 Å at 40 kV and 40 mA.

Solid-state nuclear magnetic resonance (SSNMR). All the SSNMR experiments were

performed with magic angle spinning (MAS) on a Bruker Avance II 400 MHz wide-bore

solid-state NMR spectrometer at a magnetic field of 9.4 T. 13C MAS NMR data were

acquired at the Larmor frequency (ν0) of 100.6 MHz and 29Si MAS NMR data were

acquired at ν0 of 79.5 MHz. Both the 13C and 29Si chemical shifts were referenced to

tetramethylsilane (TMS) at 0 ppm (δiso). All the 13C and 29Si experiments were carried out

on a standard 4 mm double-resonance probe with the sample spinning rate of 10 kHz. 13C

4

cross-polarization (CP) MAS experiments were carried out with a 1H π/2 pulse length of

3.2 μs, a contact time of 3 ms, a pulse delay of 3 s, and a TPPM decoupling frequency of

78.1 kHz. The 29Si CP/MAS spectra were acquired with a 1H π/2 pulse length of 4.0 μs, a

contact time of 6.5 ms, a pulse delay of 3 s, and a TPPM decoupling frequency of 62.5

kHz.

N2 adsorption-desorption analysis. The N2 adsorption-desorption experiments were

conducted on a Micromeritics ASAP 2020 Surface Area and Porosimetry Analyzer. The

sample was degassed at 120 °C for 12 h before the measurements. N2 isotherms were

recorded at 77 K by using ultra-high purity N2 (99.999% purity). Data analysis was

conducted using ASAP 2020 V4.00 software. The surface area was determined using

Brunauer-Emmett-Teller (BET) adsorption model, and the pore volume was determined

using the single point adsorption model and provided in the main text. The pore size

distribution was calculated from the adsorption isotherm by nonlocal density functional

theory (NLDFT) method and provided in the main text.

Other characterization methods. 1H and 13C liquid NMR spectra were recorded on a

Bruker Avance III 400 MHz NMR spectrometer at room temperature. The chemical

shifts are given in ppm (parts per million) relative to TMS and the coupling constants J

are given in Hz. DMSO-d6 was used as deuterated solvent. TMS served as the internal

standard (δ = 0.00 ppm) for 1H NMR, while DMSO-d6 as the internal standard (δ = 39.5

ppm) for 13C NMR. HRMS data were obtained with ESI ionization sources on a Bruker

micrOTOF Q II mass spectrometer. The elemental analyses were carried out on an

Elementar Analysensysteme GmbH vario EL cube V1.2.1 elemental analyzer. The

scanning electron microscopy (SEM) images were obtained on a Hitachi S-4800 field

emission scanning electron microscope at the accelerating voltages of 5.0 to 10.0 kV. The

optical micrographs were recorded on a Leica DM4000B microscope equipped with a

DFC420C camera. The Fourier transform infrared (FT-IR) spectra were recorded with a

Nicolet Nexus 670 FT-IR spectrometer. The thermogravimetric (TG) curves were

recorded on a Netzsch STA449C simultaneous thermal analyzer.

5

Section S2. Synthesis of COF Building Blocks and COF Crystallization

The building blocks used for synthesizing COFs, such as tetrakis(4-

aminophenyl)methane (TAM), tetrakis(4-formylphenyl)methane (TFM), and tetrakis(4-

formylphenyl)silane (TFS) were synthesized according to the reported procedures (34-

38). 4,7-bis(4-formylbenzyl)-1H-benzimidazole (BFBZ), the aldehyde monomer of LZU-

79, was synthesized according to the following procedures (Scheme S1). Polycrystalline

COF-300 was synthesized according to the reported procedure. (21).

Scheme S1. Preparation of aldehyde building block (BFBZ) for LZU-79.

4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (2)

(4-formylphenyl)boronic acid (1) (2.0 g, 13.3 mmol) and 2,3-dimethylbutane-2,3-diol

(1.6 g, 13.3 mmol) were dissolved in 20 mL Et2O in a round-bottom flask. 4 Å zeolite

(2.0 g) was dispersed to the reaction mixture. The mixture was stirred at room

temperature for 12 h. After the reaction was completed, the mixture was filtered and the

filtrate was then evaporated under reduced pressure to give 2 as a white solid. This solid

was used for the next reaction without further purification.

4,7-bis(4-formylbenzyl)-1H-benzimidazole (BFBZ).

Under argon atmosphere, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde

(2) (2.0 g, 8.6 mmol), 4,7-dibromo-1H-benzo[d]imidazole (3) (1.0 g, 3.6 mmol), K2CO3

(1.5 g, 10.8 mmol), and Pd(PPh3)4 (419.0 mg, 0.2 mmol) were added into a two-neck

flask. A degassed mixture of 1,4-dioxane (28 mL) and H2O (7 mL) was added into the

flask. The reaction mixture was stirred and refluxed at 100 °C for 24 h. After cooling to

room temperature, water was added and the organic product was extracted with ethyl

acetate. The combined organic layer was washed with brine, dried over anhydrous

Na2SO4, and then evaporated under reduced pressure to provide the crude product as a

brown solid. The crude product was purified by flash column chromatography on silica

gel using n-hexane: ethyl acetate =1: 2 as the eluent to give pure BFBZ as a yellow

powder. Yield: 51.1% (0.6 g). 1H NMR (400 MHz, DMSO-d6): δ = 12.92 (s, 1H), 10.12

(s, 1H), 10.08 (s, 1H), 8.44-8.42 (m, 3H), 8.09 (d, J = 8.0 Hz, 2H), 8.04 (d, J = 8.0 Hz,

2H), 7.95 (d, J = 8.0 Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H). 13C

NMR (100 MHz, DMSO-d6): δ = 193.3, 144.3, 144.1, 143.9, 142.0, 135.8, 135.3, 132.2,

130.7, 130.0, 129.9, 129.8, 129.4, 125.5, 123.5, 122.1. HRMS: m/z calcd. for C21H15N2O2

[M + H]+: 327.1126, found: 327.1128.

6

Crystallization of single-crystalline COF-300 with the average size of ~ 60 μm.

A vial was charged with terephthaldehyde (BDA, 12.0 mg, 0.089 mmol), aniline (0.12

mL, 15 equiv.) and 0.5 mL of 1,4-dioxane, then 0.2 mL of aqueous acetic acid (6 M) was

added to the solution. Tetrakis(4-aminophenyl)methane (TAM, 20.0 mg, 0.052 mmol)

dissolved in 1,4-dioxane (0.5 mL) was then added. Then the mixture was allowed to

further stand at ambient temperature. The single crystals of COF-300 slowly crystallized

out at ambient temperature and the crystal size reached ~60 μm within 30 to 40 days and

some crystals further reached ~100 μm in 80 days. The as-synthesized single crystals

were picked up directly for SXRD measurements. To reach a better diffraction resolution,

some of the as-synthesized crystals were immersed in 1,4-dioxane for 24 h and then in

isopropanol for 24 h to exchange out the guest molecules in the pores (such as 1,4-

dioxane, aniline, acetic acid, H2O, unreacted building blocks, etc.). Despite the increase

of diffraction resolution, the atomic positions of solvent guest molecules could not be

obtained. Part of the as-synthesized crystals were immersed in 1,4-dioxane for 24 h and

then in water for 24 h to exchange the guest molecules in the pores, and the H2O-

exchanged COF-300 crystals were also subject to the SXRD measurements. Further

activation of COF-300 was carried out by Soxhlet extraction in 1,4-dioxane for 24 h,

drying at ambient temperature for 12 h, at 100 oC for 12 h, and at 120 oC in vacuum for

12 h to afford yellow crystals. Yield: 49.8% (11.3 mg). This activated sample was then

used for a series of characterizations including elemental analysis, SEM, PXRD,

SSNMR, FT-IR, and TGA. Elemental analysis results: calcd. for C41H28N4: C 85.42%; H

4.86%; N 9.72%. Found: C 82.86%; H 5.03%; N 8.76%.

Crystallization of single-crystalline COF-300 with the average crystal size from 1 to

30 μm.

The key strategy for the controllable synthesis of COF-300 with different crystal sizes is

the addition of aniline with different quantities, which offered different degrees of

inhibition for nucleation. The typical procedure is listed as follows: vials were charged

with BDA (12.0 mg, 0.05 mmol), aniline (0.005 ~ 0.12 mL, 0.6 ~ 15 equiv.) and 0.5 mL

of 1,4-dioxane then 0.2 mL of aqueous acetic acid (6 M) was added to the solutions.

TAM (20.0 mg, 0.05 mmol) dissolved in 1,4-dioxane (0.5 mL) was then added. Mixtures

with different turbidity were obtained, which were heated further at 120 oC or left to

stand at ambient temperature for 3 ~ 10 days. The single crystals of COF-300 with

different crystal sizes then slowly crystallized out, and the crystal sizes ranged from ~ 1 ~

30 μm. Further activation for these COF-300 samples were carried out as procedures

described above to afford yellow crystals. The phase purity of these samples was then

verified by PXRD and SEM.

Crystallization of single-crystalline COF-303 with the average size of ~ 15 μm.

A vial was charged with tetrakis(4-formylphenyl)methane (TFM, 10.8 mg, 0.025 mmol),

aniline (0.12 mL, 52 equiv.), and 0.25 mL of 1,4-dioxane, then 0.1 mL of aqueous acetic

acid (6 M) was added to the solution. Phenylenediamine (PDA, 5.4 mg, 0.05 mmol)

dissolved in 1,4-dioxane (0.25 mL) was then added. Then the mixture was allowed to

further stand at ambient temperature. The single crystals of COF-303 then slowly

7

crystallized out at ambient temperature and the crystal size reached ~15 μm in 15 days.

The as-synthesized single crystals were picked up directly for SXRD measurements.

Further activation for COF-303 was carried out as procedures described above to afford

yellow crystals. Yield: 56.9% (8.2 mg). This activated sample was then used for a series

of characterizations including elemental analysis, SEM, PXRD, SSNMR, FT-IR, and

TGA. Elemental analysis results: calcd. for C41H28N4: C 85.42%; H 4.86%; N 9.72%.

Found: C 86.53%; H 4.93%; N 8.99%. The obtained new solid material was

characterized as the COF-303, which was insoluble in boiling water and common organic

solvents (such as acetone, methanol, tetrahydrofuran, and N,N-dimethylformamide).

Crystallization of single-crystalline LZU-79 with the average size of ~ 100 μm.

A vial was charged with 4,7-bis(4-formylbenzyl)-1H-benzimidazole (BFBZ, 17.0 mg,

0.052 mmol), aniline (0.12 mL, 25 equiv.) and 0.75 mL of 1,4-dioxane, then 0.2 mL of

aqueous acetic acid (6 M) was added to the solution. Tetrakis(4-aminophenyl)methane

(TAM, 10.0 mg, 0.026 mmol) dissolved in 1,4-dioxane (0.75 mL) was then added. Then

the mixture was allowed to further stand at ambient temperature. The single crystals of

LZU-79 then slowly crystallized out at ambient temperature and the crystal size reached

~50 μm in 20 days and further reached ~100 μm in 50 days. The as-synthesized single

crystals were picked up directly for SXRD measurements. To reach a better diffraction

resolution, some of the as-synthesized crystals were immersed in 1,4-dioxane for 24 h

and then in cyclohexanol for 24 h to exchange the guest molecules in the pores. The

cyclohexanol-exchanged LZU-79 crystals were also subject to SXRD measurements to

reach a resolution of 1.25 Å. Despite the increase of diffraction resolution, the atomic

positions of solvent guest molecules could not be obtained. Further activation of LZU-79

was carried out as procedures described above to afford yellow crystals. Yield: 42.6%

(10.7 mg). This activated sample was then used for a series of characterizations including

elemental analysis, SEM, PXRD, SSNMR, FT-IR, and TGA. Elemental analysis results:

calcd. for C67H40N8: C 84.08%; H 4.21%; N 11.71%. Found: C 87.17%; H 4.72%; N

11.41%. This obtained new solid material was characterized as the LZU-79, which was

insoluble in boiling water and common organic solvents (such as acetone, methanol,

tetrahydrofuran, and N,N-dimethylformamide).

Crystallization of single-crystalline LZU-111 with the average size of ~ 50 μm.

A vial was charged with tetrakis(4-formylphenyl)silane (TFS, 22.4 mg, 0.05 mmol),

aniline (0.36 mL, 80 equiv.) and 0.5 mL of 1,4-dioxane, then 0.2 mL of aqueous acetic

acid (6 M) was added to the solution. Tetrakis(4-aminophenly)methane (TAM, 19.0 mg,

0.05 mmol) dissolved in 1,4-dioxane (0.5 mL) was then added. Then the mixture was

allowed to further stand at ambient temperature. The single crystals of LZU-111 then

slowly crystallized out at ambient temperature and the crystal size reached ~45 μm in 47

days and further reached ~55 μm in 80 days. The as-synthesized single crystals were

picked up directly for SXRD measurements. To reach a better diffraction resolution,

some of the as-synthesized crystals were immersed in 1,4-dioxane or in cyclohexanol for

24 h to exchange the guest molecules in the pores. Despite the increase of diffraction

resolution, the atomic positions of solvent guest molecules could not be obtained. Further

activation of LZU-111 was carried out as procedures mentioned above to afford light

8

yellow crystals. Yield: 43.9% (16.6 mg). This activated sample was then used for a series

of characterizations including elemental analysis, SEM, PXRD, SSNMR, FT-IR, and

TGA and N2 adsorption-desorption isotherms. Elemental analysis results: calcd. for

C53H36N4Si: C 84.09%; H 4.79%; N 7.40%. Found: C 83.14%; H 4.12%; N 7.07%. The

obtained LZU-111 was insoluble in boiling water and common organic solvents (such as

acetone, methanol, tetrahydrofuran, and N,N-dimethylformamide).

Modulated crystallization of COFs with monodentate amines or aldehydes.

Substituted anilines such as cyclohexylamine, p-haloanilines, o-haloanilines, m-

haloanilines, p-methylaniline, o-toluidine, m-toluidine, p-nitroaniline, o-nitroaniline, p-

methoxyaniline were used to synthesis of different COFs, but all of them did not perform

as efficient modulators. Specifically, some substituted anilines (such as p-

methoxyaniline, p-bromoaniline, p-methylaniline etc.) first reacted with aldehyde

monomer very quickly, and their condensation products precipitated as stable and

insoluble solids. Precipitation precludes the subsequent reactions that form COFs. Thus,

these substituted anilines cannot be used to modulate the reaction. Other substituted

anilines (such as p-nitroaniline, p-iodoaniline, m-toluidine etc.) reacted with aldehyde

monomer very slowly, and their condensation products were unstable; these products

decompose back to substituted anilines and aldehyde monomer. As observed in

experiments, some precipitates were initially produced after minor addition of acid,

which are then slowly dissolved to give a homogeneous mixture. After the amine

monomer was added, precipitation of amorphous solids was observed immediately,

which is typical during the synthesis of nano-crystals. This indicates that the amine

monomer reacted with aldehyde monomer directly without any intermediacy of the

aniline. Monodentate aldehydes such as acetaldehyde, benzaldehyde or substituted

benzaldehydes (p-halobenzaldehydes, p-nitrobenzaldehyde, p-tolualdehyde) were also

investigated, but did not produce any crystalline material.

9

Section S3. Single-crystal x-ray Diffraction Analysis

COF-300. A rod-shaped crystal (60 × 20 × 20 μm3) of COF-300 was measured on a

Rigaku XtaLAB Rapid-S x-ray diffractometer with Mo Κα radiation (λ = 0.7107 Å).

According to the intensity statistics table for the whole dataset (PRP file), the resolution

was cut off to 0.85 Å. Solvent masking was applied during structure refinement (39) the

structure was refined anisotropically and hydrogen atoms were placed into positions

calculated geometrically. The connected asymmetric unit was defined inside the unit cell:

MOVE command was applied to all atoms. The weighting scheme is refined.

10

Table S1.

Crystal data, data collection, and structure refinement parameters for COF-300.

Name COF-300

Chemical composition of COF C41 H28 N4

Formula mass 576.67

Crystal system Tetragonal

Space group I41/a

a, Å 26.2260(18)

c, Å 7.5743(10)

V, Å3 5209.6(10)

d, g cm-3 0.735

μ, mm-1 0.044

Z 4

Measured reflections 28014

Independent reflections 2230

Observed reflections 976

θmin , º 3.474

θmax , º 24.727

h -30 to 29

k -30 to 29

l -8 to 8

R int 0.1857

R [F2>2σ(F2)] 0.0614

wR(F2) 0.1541

S 0.973

Parameters 102

Restraints 0

∆ρmax, e Å-3 0.146

∆ρmin, e Å-3 -0.133

Crystal size, mm3 0.060 × 0.020 × 0.020

Radiation, Å 0.71073

Temperature, K 100

CCDC number

11

Fig. S1.

Asymmetric unit in the single-crystal structure of COF-300. Thermal ellipsoids are drawn

with 50% probability.

12

COF-300 with disordered linker. A needle-shaped crystal (50 × 10 × 10 μm3) of COF-

300 was measured at beamline 11.3.1 at the ALS with radiation of = 1.2398 Å.

According to the intensity statistics table for the whole dataset (PRP file), the resolution

was cut off to 0.89 Å. Solvent masking was applied during structure refinement. The

structure was refined anisotropically and hydrogen atoms were placed into positions

calculated geometrically. The connected asymmetric unit was defined inside the unit cell:

MOVE command was applied to all atoms. The weighting scheme is refined.

13

Table S2.

Crystal data, data collection, and structure refinement parameters for COF-300 with

disordered linker.

Name COF-300_disordered


Formula mass 576.67


Space group I41/a

a, Å 26.3138(18)

c, Å 7.5716(10)

V, Å3 5242.7(4)

d, g cm-3 0.731

μ, mm-1 0.170

Z 4




θmin , º 2.701

θmax , º 44.119

h -28 to 29

k -29 to 27

l -8 to 8

R int 0.0510

R [F2>2σ(F2)] 0.0761

wR(F2) 0.2068

S 1.114

Parameters 121

Restraints 0

∆ρmax, e Å-3 0.255

∆ρmin, e Å-3 -0.177

Crystal size, mm3 0.050 × 0.010 × 0.010


Temperature, K 100

CCDC number

14

Fig. S2.

Asymmetric unit in the single-crystal structure of COF-300 with the disordered linker.

Thermal ellipsoids are drawn with 50% probability.

15

Fig. S3.

Single-crystal structure of COF-300 viewed along c-axis. C atoms, grey; N atoms, blue.

H atoms were omitted for clarity.

16

Hydrated COF-300. A needle-shaped crystal (60 × 10 × 10 μm3) of hydrated COF-300

was measured at beamline 11.3.1 at the ALS with radiation of = 1.0332 Å. According

to the intensity statistics table for the whole dataset (PRP file), the resolution was cut off

to 0.83 Å. Solvent masking was not applied during structure refinement. The structure

was refined anisotropically and hydrogen atoms were placed into positions calculated

geometrically. The connected asymmetric unit was defined inside the unit cell: MOVE

command was applied to all atoms. The weighting scheme is refined as well as the

extinction coefficient.

17

Table S3.

Crystal data, data collection, and structure refinement parameters for hydrated COF-300.

Name Hydrated COF-300


Chemical formula of guests H2O (8 molecules)

Formula mass 1297.47


Space group I41/a

a, Å 19.6394(6)

c, Å 8.9062(15)

V, Å3 3435.2(4)

d, g cm-3 1.254

μ, mm-1 0.200

Z 2




θmin , º 3.016

θmax , º 38.508

h -22 to 23

k -17 to 23

l -10 to 10

R int 0.0687

R [F2>2σ(F2)] 0.0903

wR(F2) 0.2323

S 1.101

Parameters 114

Restraints 0

∆ρmax, e Å-3 0.286

∆ρmin, e Å-3 -0.346

Crystal size, mm3 0.060 × 0.010 × 0.010


Temperature, K 100

CCDC number

18

Fig. S4.

Asymmetric unit in the single-crystal structure of hydrated COF-300. Thermal ellipsoids

are drawn with 50% probability.

19

Fig. S5.

Single-crystal structure of hydrated COF-300 viewed along c-axis. C atoms, grey; N

atoms, blue; O atoms, red; H atoms, white. H-bonds, light blue dashed line. H atoms in

the framework of COF-300 were omitted for clarity.

20

COF-303. A needle-shaped crystal (40 × 10 × 10 μm3) of COF-303 was measured at

beamline 11.3.1 at the ALS with radiation of = 1.2399 Å. According to the intensity

statistics table for the whole dataset (PRP file), the resolution was cut off to 1.10 Å.

Solvent masking was applied during structure refinement. The structure was refined

anisotropically and hydrogen atoms were placed into positions calculated geometrically.

The connected asymmetric unit was defined inside the unit cell: MOVE command was

applied to all atoms. The weighting scheme is refined as well as the extinction

coefficient.

21

Table S4.

Crystal data, data collection, and structure refinement parameters for COF-303.

Name COF-303


Formula mass 576.67


Space group I41/a

a, Å 26.47(3)

c, Å 7.449(9)

V, Å3 5220(13)

d, g cm-3 0.734

μ, mm-1 0.171

Z 4




θmin , º 2.684

θmax , º 34.152

h -23 to 23

k -23 to 23

l -6 to 6

R int 0.1425

R [F2>2σ(F2)] 0.1737

wR(F2) 0.4198

S 1.512

Parameters 103

Restraints 18

∆ρmax, e Å-3 0.442

∆ρmin, e Å-3 -0.439

Crystal size, mm3 0.040 × 0.010 × 0.010


Temperature, K 100

CCDC number

22

Fig. S6.

Asymmetric unit in the single-crystal structure of COF-303. Thermal ellipsoids are drawn

with 50% probability.

23

Fig. S7.

Single-crystal structure of COF-303 viewed along c-axis. C atoms, grey; N atoms, blue.

H atoms were omitted for clarity.

24

The imine connectivity in both COF-300 and COF-303 is the only structural difference

between these frameworks. This minor difference can be distinguished by comparison of

torsion angles in aniline (C−C=N−C torsion angle) and benzylidene (C−C−C=N torsions

angle) moieties. In addition, the values for torsion angles for the molecular analog

benzylideneaniline are listed (24).

Table S5.

Torsion angles in COF-300, COF-303 and their molecular analog.

COF-300 COF-303 Molecular analog

Aniline -34.6(4)° -62(2)° 55°

Benzylidene -7.4(5)° 9(2)° 10°

25

LZU-79. A needle-shaped crystal (100 × 20 × 20 μm3) of LZU-79 was measured at

beamline BL17B1 at the SSRF with radiation of λ = 0.9840 Å. According to the intensity

statistics table for the whole dataset (PRP file), the resolution was cut off to 1.25 Å.

Solvent masking was applied during structure refinement. The connected asymmetric unit

was defined inside the unit cell: MOVE command was applied to all atoms. The

weighting scheme is refined as well as the extinction coefficient. The initial structure

model of LZU-79 was established via the direct determination of the quaternary carbon

positions from SHELXS. The structure was refined isotropically and hydrogen atoms

were placed into positions calculated geometrically. The phenyl groups were refined as

rigid bodies. Due to the weak intensity and disorder of solvent molecules in the pore, the

final refinement converged at relatively large R-values.

26

Table S6.

Crystal data, data collection, and structure refinement parameters for LZU-79.

Name LZU-79


Formula mass 957.07


Space group P42/n

a, Å 27.838(2)

c, Å 7.5132(12)

V, Å3 5822.4(13)

d, g cm-3 0.546

μ, mm-1 0.069

Z 2




θmin , º 3.204

θmax , º 23.177

h -22 to 21

k -22 to 22

l -6 to 5

R int 0.2289

R [F2>2σ(F2)] 0.4767

wR(F2) 0.7813

S 2.572

Parameters 31

Restraints 28

∆ρmax, e Å-3 1.164

∆ρmin, e Å-3 -0.932

Crystal size, mm3 0.1 × 0.020 × 0.020


Temperature, K 100

CCDC number

27

Fig. S8.

Asymmetric unit in the single-crystal structure of LZU-79.

28

Fig. S9.

Single-crystal structure of LZU-79 viewed along c-axis. C atoms, grey; N atoms, blue. H

atoms were omitted for clarity.

29

LZU-111. The laboratory SXRD data of LZU-111 were collected on an Agilent

SuperNova diffractometer with Cu Κα radiation (λ = 1.5418 Å). The unit cell parameters

were initially determined from 263 reflections. The whole dataset had a relatively low

resolution (~1.8 Å), which was not enough for the structure refinement. Thus, a

hexagonal prism-shaped crystal (60 × 50 × 30 μm3) of LZU-111 was measured at

beamline BL17B1 of the SSRF with radiation of λ = 0.9786 Å. According to the intensity

statistics table for the whole dataset (PRP file), the resolution was cut off to 1.20 Å. The

initial structure model of LZU-111 was established via the direct determination of the Si

positions from SHELXS. The phenyl groups were refined as rigid bodies. The structure

was refined isotropically, except for silicon atoms, which were refined anisotropically,

and hydrogen atoms were placed into positions calculated geometrically. Solvent

masking was applied during structure refinement. The connected asymmetric unit was

defined inside the unit cell: MOVE command was applied to all atoms. The weighting

scheme is refined as well as the extinction coefficient.

30

Table S7.

Crystal data, data collection, and structure refinement parameters for LZU-111.

Name LZU-111

Chemical composition of COF C53 H36 N4 Si

Formula mass 756.96

Crystal system Hexagonal

Space group P65

a, Å 20.3958(4)

c, Å 33.7704(18)

V, Å3 12166.0(8)

d, g cm-3 0.620

μ, mm-1 0.111

Z 6




θmin , º 2.297

θmax , º 24.060

h -16 to 16

k -16 to 16

l -28 to 28

R int 0.0717

R [F2>2σ(F2)] 0.1737

wR(F2) 0.4232

S 1.826

Parameters 526

Restraints 418

Flack parameter 0.20(3)

∆ρmax, e Å-3 0.272

∆ρmin, e Å-3 -0.206

Crystal size, mm3 0.060 × 0.050 × 0.030


Temperature, K 100

CCDC number

31

Fig. S10.

Asymmetric unit in the single-crystal structure of LZU-111. Thermal ellipsoids are drawn

with 50% probability. Hydrogen atoms are omitted for clarity.

32

Fig. S11.

Single-crystal structure of LZU-111 viewed along c-axis. C atoms, grey; N atoms, blue;

Si atoms, yellow. H atoms were omitted for clarity.

33

Section S4. Powder x-ray Diffraction Analysis

COF-300. PXRD data were collected on a PANalytical X’Pert Pro diffractometer with

Cu Kα radiation of λ = 1.5418 Å at 40 kV and 40 mA. Prior to analysis, the samples were

ground and mounted on flat sample holders. The samples were then measured with a

Bragg angle (2θ) range of 5.0º to 50.0º using a step size of 0.0167º and a scan time of 2 s

per step.

The intense background at 2θ range of 17.5º to 27.5º in the powder pattern of 1,4-

dioxane-exchanged COF-300 was caused by the large quantity of liquid 1,4-dioxane.

Similarly, the background in the powder pattern of hydrated COF-300 was caused by

large quantity of liquid H2O. The calculated PXRD pattern according to the “solvent-

masked” single-crystal structure of COF-300 are in light brown; the calculated PXRD

pattern for hydrated COF-300 according to the hydrated single-crystal structure of COF-

300 is in purple. The intensity values along the Y−axis were normalized for comparison.

The PXRD pattern of single-crystal COF-300 is different from those of the building

blocks, indicating that a new crystalline phase has been formed. As confirmed by SXRD,

the structure transformation of single-crystal COF-300 was also indicated by PXRD, as

shown in patterns of different solvated COF-300 samples and activated COF-300. This

kind of structure transformation is reversible.

34

Fig. S12.

PXRD patterns of BDA, red; TAM, blue; single-crystalline COF-300 with the crystal size

of ~ 60 μm washed with 1,4-dioxane, turquoise; hydrated COF-300 form, pink; activated

COF-300, black.

35

COF-303. PXRD data were collected on a PANalytical X’Pert Pro diffractometer with

Cu Kα radiation of λ = 1.5418 Å at 40 kV and 40 mA. Prior to analysis, the samples were

ground and mounted on flat sample holders. The samples were then measured with a


per step.

The intense background at 2θ range of 17.5º to 27.5º in the powder pattern of 1,4-

dioxane-exchanged COF-303 was caused by the large quantity of liquid 1,4-dioxane. The

calculated PXRD pattern according to the “solvent-masked” single-crystal structure of

COF-303 is in light brown. The intensity values along the Y−axis were normalized for

comparison. The PXRD patterns of single-crystal COF-303 samples are different from

those of the building blocks, indicating that a new crystalline phase has been formed.

36

Fig. S13.

PXRD patterns of TFM, red; PDA, blue; single-crystalline COF-303 with the crystal size

of ~ 15 μm washed with 1,4-dioxane, turquoise; activated COF-303, black.

37

LZU-79. PXRD data were collected on a PANalytical X’Pert Pro diffractometer with Cu

Kα radiation of λ = 1.5418 Å at 40 kV and 40 mA. Prior to analysis, the samples were

ground and mounted on flat sample holders. The samples were then measured with the


per step.

The intense background at 2θ range of 17.5º to 27.5º in the powder pattern of 1,4-dioxane

exchanged LZU-79 was caused by the large quantity of liquid 1,4-dioxane. The

calculated PXRD pattern according to the “solvent-masked” single-crystal structure of

LZU-79 is in light brown. The intensity values along the Y−axis were normalized for

comparison. The PXRD patterns of single-crystal LZU-79 samples are different from

those of the building blocks, indicating that a new crystalline phase has been formed. The

background from 2θ = 17.5º ~ 27.5º in the pattern of activated LZU-79 may be caused by

disorder in structure after the sustaining guest molecules were removed.

38

Fig. S14.

PXRD patterns of BFBZ, red; TAM, blue; single-crystalline LZU-79 with the crystal size

of ~ 100 μm washed with 1,4-dioxane, turquoise; activated LZU-79, black.

39

LZU-111. PXRD data were collected on a PANalytical X’Pert Pro diffractometer with Cu

Kα radiation of λ = 1.5418 Å at 40 kV and 40 mA. Prior to analysis, the samples were

ground and mounted on flat sample holders. The samples were then measured with the


per step.

The intense background of 2θ range of 17.5º to 27.5º in the powder pattern of 1,4-dioxane-

exchanged LZU-111 was caused by the large quantity of liquid 1,4-dioxane. The calculated

PXRD pattern according to the “solvent-masked” single-crystal structure of LZU-111 is in

light brown. The intensity values along the Y−axis were normalized for comparison. No

peaks after 2θ = 35.0º was observed in the experimental pattern of LZU-111. The PXRD

patterns of single-crystal LZU-111 samples are different from those of the building blocks,

indicating that a new crystalline phase has been formed. No obvious structure

transformation between solvated and activated samples is apparent from PXRD patterns.

40

Fig. S15.

PXRD patterns of TFS, red; TSM, blue; single-crystalline LZU-111 with the crystal size

of ~ 30 μm washed with 1,4-dioxane, turquoise; activated LZU-111, black.

41

Section S5. Solid-state Nuclear Magnetic Resonance Spectroscopic Analysis

COF-300. The 13C CP/MAS measurements of BDA, TAM and activated COF-300 were

carried out on a standard 4 mm double-resonance probe with the sample spinning rate of

10 kHz. The assignments for 13C NMR signals are shown as insets. Asterisks denote the

spinning sidebands. The 13C CP/MAS NMR signal of the BDA at 195 ppm correspond to

the carbon atoms at the terminal aldehyde groups (−CHO), and the signal of the TAM at

64 ppm corresponds to the quaternary carbon atoms. The signal of −CHO disappeared

and the signal of quaternary carbon atoms appeared in the 13C CP/MAS NMR spectrum

of COF-300, indicating that the two building blocks have reacted to form COF-300. In

addition, new signals appear in the 13C CP/MAS NMR spectrum of COF-300 at 155 and

159 ppm, which offer direct evidence for the successful formation of imine bonds

(−C=N−) throughout the COF-300 framework.

42

Fig. S16. 13C CP/MAS spectra of BDA, red; TAM, blue; single-crystal of COF-300 with crystal

size of ~ 60 μm, black.

43

COF-303. The 13C CP/MAS experiments of TFM, PDA and activated COF-303 were



spinning sidebands. The 13C CP/MAS NMR signal of the TFM at 192 ppm correspond to

the carbon atoms at the terminal aldehyde groups (−CHO), and the signal of the TFM at

67 ppm corresponds to the quaternary carbon atoms. The signal of −CHO disappeared

and the signal of quaternary carbon atoms appeared in the 13C CP/MAS NMR spectrum

of COF-303, indicating that the two building blocks have reacted to form COF-303. In

addition, a new signal at 158 ppm appears in the 13C CP/MAS NMR spectrum of COF-

303, which offers direct evidence for the successful formation of imine bonds (−C=N−)

throughout the COF-303 framework.

44

Fig. S17. 13C CP/MAS spectra of the TFM, red; PDA, blue; and the single-crystal of COF-303 with

crystal size of ~ 15 μm, black.

45

LZU-79. The 13C CP/MAS experiments of BFBZ, TAM and activated LZU-79 were



spinning sidebands. The 13C CP/MAS NMR signal of the BFBZ at 192 and 198 ppm

correspond to the carbon atoms at the terminal aldehyde groups (−CHO), and the signal

of the TAM at 64 ppm corresponds to the quaternary carbon atoms. The signal of −CHO

disappeared and the signal of quaternary carbon atoms appeared in the 13C CP/MAS

NMR spectrum of LZU-79, indicating that the two building blocks have reacted to form

LZU-79. In addition, a new signal appears at 160 ppm in the 13C CP/MAS NMR

spectrum of LZU-79, which offer direct evidence for the successful formation of imine

bonds (−C=N−) throughout the LZU-79 framework.

46

Fig. S18. 13C CP/MAS spectra of BFBZ, red; TAM, blue; and the single-crystal LZU-79 with


47

LZU-111. The 13C CP/MAS experiments of TFS, TAM and activated LZU-111 were



spinning sidebands. The 13C CP/MAS NMR signals of the TFS at 190, 194 ppm

correspond to the carbon atoms at the terminal aldehyde groups (−CHO), and the signal

of the TAM at 64 ppm corresponds to the quaternary carbon atoms. The signal of −CHO

disappeared and the signal of quaternary carbon atoms appeared in the 13C CP/MAS

NMR spectrum of LZU-111, indicating that the two building blocks have reacted to

formLZU-111. In addition, a new signal appears at 158 ppm in the 13C CP/MAS NMR

spectrum of LZU-111, which offer direct evidence for the successful formation of imine

bonds (−C=N−) throughout the LZU-111 framework.

The 29Si CP/MAS experiments of TFS and activated LZU-111 were carried out on a

standard 4 mm double-resonance probe with the sample spinning rate of 10 kHz. The

appearance of the 29Si NMR signals at −14 ppm in both spectra indicates that the LZU-

111 framework has been successfully formed.

48

Fig. S19. 13C CP/MAS spectra of TFS, red; TAM, blue; and the single-crystal of LZU-111 with


49

Fig. S20. 29Si CP/MAS spectra of the TFS, red; and the single-crystal LZU-111 with crystal size of

~ 30 μm, black.

50

Section S6. Fourier Transform Infrared Spectroscopic Analysis

COF-300. FT-IR spectra of BDA, TAM and activated COF-300 were obtained with KBr

pellets. The transmittance values along the Y−axis were normalized for comparison. A

appearance of a new −C=N− stretching vibration band at 1616 cm-1 in the FT-IR

spectrum of COF-300 is direct evidence for the successful formation of imine bonds

throughout the COF-300 framework. Meanwhile, no bands for the terminal −CHO (at

1693 cm-1) or −NH2 (at 3396 and 3172 cm-1) groups could be observed, indicating the

structural regularity of COF-300 with very few defects.

51

Fig. S21.

FT-IR spectra of BDA, red; TAM, blue; and the single-crystal COF-300 with crystal size

of ~ 60 μm, black.

52

COF-303. FT-IR spectra of TFM, PDA and activated COF-303 were obtained with KBr

pellets. The transmittance values along the Y−axis were normalized for comparison. The


spectrum of COF-303 is direct evidence for the successful formation of imine bonds

throughout the COF-303 framework. Meanwhile, no bands for the terminal −CHO (at


structural regularity of single-crystal COF-303 with very few defects.

53

Fig. S22.

FT-IR spectra of TFM, red; PDA, blue; and the single-crystal COF-303 with crystal size

of ~ 15 μm, black.

54

LZU-79. FT-IR spectra of BFBZ, TAM and activated LZU-79 were obtained with KBr



spectrum of LZU-79 (black) is direct evidence for the successful formation of imine

bonds throughout the LZU-79 framework. Meanwhile, no bands for the terminal −CHO

(at 1693 cm-1) or −NH2 (at 3396 and 3172 cm-1) groups could be observed, indicating the

structural regularity of LZU-79 with very few defects.

55

Fig. S23.

FT-IR spectra of BFBZ, red; TAM, blue; and the single-crystal LZU-79 with crystal size

of ~ 100 μm, black.

56

LZU-111. FT-IR spectra of TFS, TAM and activated LZU-111 were obtained with KBr



spectrum of LZU-111 is direct evidence for the successful formation of imine bonds

throughout the LZU-111 framework. Meanwhile, no bands for the terminal −CHO (at


structural regularity of LZU-111 with very few defects.

57

Fig. S24.

FT-IR spectra of TAM, blue; TFS, red; and the single-crystal LZU-111 with crystal size

of ~ 30 μm, black.

58

Section S7. Thermogravimetric Analysis

COF-300. The TG curve of COF-300 was recorded on a Netzsch STA449C simultaneous

thermal analyzer under nitrogen atmosphere. The activated COF-300 sample was heated

from ambient temperature to 800 °C with a heating rate of 10.0 °C min-1. The

decomposition temperature of COF-300 is 522 oC for the 60 μm-sized single-crystalline

sample.

Fig. S25.

TG curve of single-crystalline COF-300.

59

COF-303. The TG curve of COF-303 was recorded on a Netzsch STA449C simultaneous

thermal analyzer under nitrogen atmosphere. The activated COF-303 sample was heated


decomposition temperature of COF-303 is 531 oC for the 15 μm-sized single-crystalline

sample.

Fig. S26.

TG curve of single-crystalline COF-303.

60

LZU-79. The TG curve of LZU-79 was recorded on a Netzsch STA449C simultaneous

thermal analyzer under nitrogen atmosphere. The activated LZU-79 sample was heated


decomposition temperature of LZU-79 is 491 oC for the 100 μm-sized single-crystalline

sample.

Fig. S27.

TG curve of single-crystalline LZU-79.

61

LZU-111. The TG curve of LZU-111 was recorded on a Netzsch STA449C simultaneous

thermal analyzer under nitrogen atmosphere. The activated LZU-111 sample was heated


decomposition temperature of LZU-111 is 556 oC for the 30 μm-sized single-crystalline

sample.

Fig. S28.

TG curve of single-crystalline LZU-111.

62

Section S8. N2 Adsorption-desorption Analysis

The N2 adsorption–desorption measurements of LZU-111 were conducted at 77 K on a

Micromeritics ASAP 2020 Surface Area and Porosimetry Analyzer. The isotherm is

shown in the main text (Fig. 4B).

Fig. S29.

BET plot for LZU-111 calculated from nitrogen adsorption data.

63

Fig. S30.

N2 isotherm of LZU-111 measured at 77 K used for NLDFT modeling and pore size

distribution calculations.

64

Fig. S31.

Views of the simulated pore structure of LZU-111. Performed with the UCSF CHIMERA

software (version 1.11), the simulations are based on the single-crystal structure of LZU-

111. a) aerial view; b) view along a−axis; c) view along c−axis; d) 3D view along a−axis.

It can be seen that LZU-111 possesses abundant pores within the regular pore structure.

The pore size (~11 Å) is fully consistent with that determined from the N2 adsorption-

desorption analyses (10.9 Å).

65

Section S9. Scanning Electron Microscopy Images

Fig. S32.

SEM image of single-crystalline COF-300 with average size of ~ 60 μm.

66

Fig. S33

SEM image of single-crystalline COF-303 with average size of ~ 10 μm.

67

Fig. S34

SEM image of single-crystalline LZU-79 with average size of ~ 100 μm.

68

Fig. S35

SEM image of single-crystalline LZU-111 with average size of ~ 50 μm.

www.sciencemag.org/content/361/6397/48/suppl/DC1

Supplementary Materials for

Single-crystal x-ray diffraction structures of covalent organic frameworks

Tianqiong Ma*, Eugene A. Kapustin*, Shawn X. Yin, Lin Liang, Zhengyang Zhou, Jing Niu, Li-Hua Li, Yingying Wang, Jie Su, Jian Li, Xiaoge Wang, Wei David Wang, Wei Wang†,

Junliang Sun†, Omar M. Yaghi†

*These authors contributed equally to this work. †Corresponding author. Email: [email protected] (W.W.); [email protected] (J.S.)

[email protected] (O.M.Y.)

Published 6 July 2018, Science 361, 48 (2018) DOI: 10.1126/science.aat7679

This PDF file includes:

Materials and Methods Supplementary Text Figs. S1 to S35 Tables S1 to S7 References

Other Supplementary Materials for this manuscript include the following: (available at www.sciencemag.org/content/361/6397/48/suppl/DC1)

Data file S1. CIF file for COF-300 Checkcif report for COF-300 (PDF) Data file S2. CIF file for COF-300_disorder Checkcif report for COF-300_disorder (PDF) Data file S3. CIF file for hydrated COF-300 Checkcif report for hydrated COF-300 (PDF) Data file S4. CIF file for LZU-79 Checkcif report for LZU-79 (PDF) Data file S5. CIF file for LZU-111 Checkcif report for LZU-111 (PDF)

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