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30
Electronic Supplementary Information Highly Photoluminescent Two Dimensional Imine-based Covalent Organic Framework for Chemical Sensing Qiang Gao, a,b,§ Xing Li, b,§ Guo-Hong Ning, b Kai Leng, b Bingbing Tian, a,b Cuibo Liu, a,b Wei Tang, c Hai-Sen Xu b and Kian Ping Loh *,a,b a SZU-NUS Collaborative Innovation Center for Optoelectronic Science & Technology, Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China b Department of Chemistry, Centre for Advanced 2D Materials (CA2DM), National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore c Institute of Materials Research and Engineering, A*STAR, 2 Fusionopolis Way, Innovis, Singapore 138634, Singapore. § These authors contributed equally to this work. *Corresponding author: Professor Kian Ping Loh (e-mail: [email protected] ) I. General Procedure-------------------------------------------------------------------------------------------S1 II. Synthesis of TPE Building Units and Model Compounds --------------------------------------------S3 III. Synthesis of Py-TPE-COF, Py-COF and TPE-COF --------------------------------------------------S4 IV. Solid-state NMR of Py-TPE-COF --------------------------------------------------------------------S10 V. Thermogravimetric analysis of Py-TPE-COF---------------------------------------------------------S11 VI. FT-IR spectra of model compounds and Py-TPE-COF --------------------------------------------S12 VII. Gas sorption data of Py-TPE-COF-------------------------------------------------------------------S13 VIII. Photoluminescence image of Py-TPE-COF, model compounds, reference imine COFs----S16 IX. UV-VIS spectra and PLQY data of Py-TPE-COF --------------------------------------------------S18 X. SEM and TEM image of Py-TPE-COF ----------------------------------------------------------------S24 XI. Structure Modelling of Py-TPE-COF-----------------------------------------------------------------S25 XII. References-----------------------------------------------------------------------------------------------S29 Electronic Supplementary Material (ESI) for ChemComm. This journal is © The Royal Society of Chemistry 2018

Transcript of Electronic Supplementary Information Highly ... · Electronic Supplementary Information Highly...

Electronic Supplementary Information

Highly Photoluminescent Two Dimensional Imine-based

Covalent Organic Framework for Chemical Sensing

Qiang Gao,a,b,§ Xing Li,b,§ Guo-Hong Ning,b Kai Leng,b Bingbing Tian,a,b Cuibo Liu,a,b Wei Tang,c

Hai-Sen Xub and Kian Ping Loh*,a,b

a SZU-NUS Collaborative Innovation Center for Optoelectronic Science & Technology, Key

Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong

Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China

b Department of Chemistry, Centre for Advanced 2D Materials (CA2DM), National University of

Singapore, 3 Science Drive 3, Singapore 117543, Singapore

c Institute of Materials Research and Engineering, A*STAR, 2 Fusionopolis Way, Innovis,

Singapore 138634, Singapore.

§ These authors contributed equally to this work.

*Corresponding author: Professor Kian Ping Loh (e-mail: [email protected] )

I. General Procedure-------------------------------------------------------------------------------------------S1

II. Synthesis of TPE Building Units and Model Compounds --------------------------------------------S3

III. Synthesis of Py-TPE-COF, Py-COF and TPE-COF --------------------------------------------------S4

IV. Solid-state NMR of Py-TPE-COF --------------------------------------------------------------------S10

V. Thermogravimetric analysis of Py-TPE-COF---------------------------------------------------------S11

VI. FT-IR spectra of model compounds and Py-TPE-COF --------------------------------------------S12

VII. Gas sorption data of Py-TPE-COF-------------------------------------------------------------------S13

VIII. Photoluminescence image of Py-TPE-COF, model compounds, reference imine COFs----S16

IX. UV-VIS spectra and PLQY data of Py-TPE-COF --------------------------------------------------S18

X. SEM and TEM image of Py-TPE-COF ----------------------------------------------------------------S24

XI. Structure Modelling of Py-TPE-COF-----------------------------------------------------------------S25

XII. References-----------------------------------------------------------------------------------------------S29

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2018

S1

I. General Procedure All starting materials are commercially available (purchased from Sigma Aldrich or TCI) and

were used as received unless specifically mentioned.

Thermogravimetric analysis (TGA): TGA was performed on a TGA 500 thermogravimetric

analyzer by heating the samples at 5 ºC min-1 to 800 ºC in a nitrogen atmosphere.

Fourier transform infrared (FT-IR): Fourier transform infrared spectra were recorded as KBr-pellet

on a Bruker OPUS/IR PS15 spectrometer.

UV-vis absorption spectra (UV): UV-vis spectra were performed by using Shimadzu UV-3600 UV-

VIS-NIR Spectrophotometer.

Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) : SEM

imaging of the Py-TPE-COF pristine materials were performed using a JEOL JSM-6701F Field-

Emission. TEM analysis was performed on an FEI Titan 80-300 S/TEM (Scanning /Transmission

Electron Microscope) operated at 200 kV.

Powder X-ray Diffraction (PXRD) measurements: PXRD studies were performed on Wide-angle

X-ray diffraction (XRD) patterns were collected on Bruker D8 Focus Powder X-ray diffractometer

using Cu Kα radiation (40 kV, 40 mA) at room temperature.

Gas Sorption measurements: Gas sorption analyses were performed by using Quantachrome

Instruments Autosorb-iQ (Boynton Beach, Florida USA) with extra-high pure gases. The samples

were activated and outgassed at 120 ºC for 8 h before the measurements. The Brunauer-Emmett-

Teller (BET) surface area and total pore volume were calculated from the N2 sorption isotherms at

77 K, and the pore size distribution was calculated based on the N2 sorption isotherm by using Non-

Local Density Functional Theory (NL-DFT, a carbon model containing slit/cylindrical pore) model

in the Quantachrome ASiQwin 5.0 software package.

Nuclear Magnetic Resonance spectroscopy (NMR):1H and 13C NMR spectra were recorded on a

Bruker AVIII (400MHz) NMR spectrometer. Chemical shifts were reported in parts per million

(ppm), and the residual solvent peak was used as an internal reference: proton (chloroform δ 7.26),

carbon (chloroform δ 77.0) was used as a reference. Data are reported as follows: chemical shift,

multiplicity (s = singlet, d = doublet), coupling constants (Hz) and integration. Solid-state 13C cross-

polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR): Solid-state

CP/MAS NMR measurement was conducted using a BRUKER DRX400WB solid-state NMR

spectrometer, 4mm CPMAS probe, 100 MHz NMR spectrometer with spin rate as 8000 MHz.

High resolution mass spectra (HRMS): HRMS was obtained on Bruker micrOTOF-Q II coupled

with a Dionex Ultimate 3000 RSLC system and Kd Science Syringe pump infusion system.

Fluorescence Quantum Yield & Lifetime:The fluorescence data and lifetimes were measured using

a Horiba Fluorolog-3 spectrofluorometer equipped with a 374 nm nanoLED for excitation and a

S2

FluoroHub R-928 detector. Absolute quantum yields (ΦF) were measured on the HORIBA

Fluorolog-3 Photon Counting Spectrofluorometer System with Quanta-φ 6-inch integrating sphere.

Structural Modeling Method:

Molecular modeling and Pawley refinement were carried out using Reflex, a software package for

crystal determination from Powder XRD pattern, implemented in BIOVIA Materials Studio

modeling version, 2016 (Dassault System). The unit cells for Py-TPE-COF based on the space group

C2/m were established, the lattice model was geometry optimized using the MS Forcite molecular

dynamics module (ultra-fine, Universal force fields, Ewald summations). Finally, Pawley

refinement was performed to optimize the lattice parameters until the RWP value converges. The

pseudo-Voigt profile function was used for whole profile fitting and Berrar–Baldinozzi function

was used for asymmetry correction during the refinement processes.

S3

II. Synthesis of Building Blocks and Model Compounds (1-5):

Figure S1. Chemical structure of monomer Py-4PhNH2 (1), monomer TPE-4CHO (2), pyrene model compound

Py-M (3) and TPE model compound TPE-M (4).

1, 3, 6, 8-tetrakis(4-aminophenyl)pyrene (1)1, pyrene model compound (Py-M, 3)1 and TPE model

compound (TPE-M, 4)2 were synthesized via the methods reported with slight modifications,

respectively. 1, 1, 2, 2‐tetrakis(4‐formylphenyl)ethane (TPE-4CHO, 2) were synthesized in

accordance to literature reported method3.

S4

III. Synthesis of Py-TPE-COF, Py-COF and TPE-COF

a) Synthesis of Py-TPE-COF

Figure S2. Synthesis routine of COF material Py-TPE-COF.

1, 3, 6, 8-tetrakis(4-aminophenyl)pyrene (1, 22.7 mg, 0.04mmol) and 1, 1, 2, 2‐tetrakis(4‐

formylphenyl)ethane (2, 17.9 mg, 0.04 mmol) were placed in a 10 mL SynthwareTM schlenk storage

tube, then the mixture was dissolved in solvent (2 mL, o-dichlorobenzene:n-butanol=1 : 1, V/V).

After sonicated for 10 minutes, aqueous 0.2 mL 6M HOAc was added, and the mixture was degassed

by three freeze-pump-thaw cycles. Finally, the tube was sealed via the screw cap, heated at 120 ℃

in an oven, and left undisturbed for 7 days. To make sure the total removal of soluble fragments or

monomers, the obtained precipitate was then immersed and washed in DMF three times, following

by the Soxhlet extraction for 24h, using THF solvent. Then the powder was dried at 120 ℃ under

vacuum for 24 h. A yellow powder was obtained in 89% isolation yield. Anal. Calcd. for [C70H42N4]n:

C, 89.53; H, 4.51; N, 5.97. Found: C, 87.24; H, 4.30; N, 5.81.

S5

Figure S3. Powder XRD patterns of Py-TPE-COF materials under different solvent conditions.

S6

b) Synthesis of Py-COF:

Py-COF was synthesized in accordance to literature reported method with slight modifications1:

Figure S4. Synthesis of Py-COF.

Py-COF: 1, 3, 6, 8-tetrakis(4-aminophenyl)pyrene (1, 22.7 mg, 0.04mmol) and terephthalaldehyde

(10.8 mg, 0.08 mmol) were placed in a 10 mL SynthwareTM schlenk storage tube, then the mixture

was dissolved in a mixture solvent (2 mL, mesitylene:1, 4-dioxane=2:1, V:V). After sonicated

for 10 minutes, aqueous 0.2 mL 6M HOAc was added, and the mixture was degassed by three

freeze-pump-thaw cycles. Finally, the tube was sealed via the screw cap, heated at 120 ℃ in an

oven, and left undisturbed for 7 days. The precipitate was filtered through centrifugation, which was

washed with anhydrous THF and DMF for 6 times, respectively. Then the precipitate was immersed

in DMF (HPLC Grade) for 3 days. To make sure the total removal of soluble fragments or monomers,

the obtained powder was extracted by Soxhlet extraction for 24h, using THF solvent. Then the

powder was dried at 120 ℃ under vacuum for 24 h.

S7

Figure S5. Powder XRD pattern of COF material Py-COF, the PXRD peeks consist with the reported Py-1P COF1.

S8

c) Synthesis of TPE-COF:

TPE-COF2,4 was synthesized in accordance to literature reported method with slight modifications:

Figure S6. Synthesis of TPE-COF

TPE-COF: 1, 1, 2, 2‐Tetrakis(4-‐aminophenyl)ethane (15.68 mg, 0.04 mmol) and

terephthalaldehyde (10.8 mg, 0.08 mmol) were placed in a 10 mL SynthwareTM schlenk storage

tube, then the mixture was dissolved in 2 mL 1, 4-dioxane. After sonicated for 10 minutes, aqueous

0.2 mL 6M HOAc was added, and the mixture was degassed by three freeze-pump-thaw cycles.

Finally, the tube was sealed via the screw cap, heated at 120 ℃ in an oven, and left undisturbed for

4 days. The precipitate was collected through centrifugation, which was washed with anhydrous

THF for 6 times, and then dried at 120 ℃ under vacuum for 24 h.

S9

Figure S7. Powder XRD pattern of COF material TPE-COF, the PXRD peeks consist with the reported TPE-

COF2,4.

S10

IV. Solid-state NMR of Py-TPE-COF

Figure S8. 13C CP/MAS NMR spectrum of Py-TPE-COF. The asterisks denote the spinning sidebands. The

assignments of 13C chemical shifts were indicated in the chemical structure.

S11

V. Thermogravimetric analysis of Py-TPE-COF

Figure S9. TGA data of Py-TPE-COF, thermally stable up to 400 °C.

S12

VI. FT-IR spectra of model compounds and Py-TPE-COF

Figure S10. FT-IR spectra of Py-TPE-COF (blue), model compound TPE-M (green), model compound Py-M (pink),

monomer Py-4PhNH2 (red) and monomer TPE-4CHO (black). The FT-IR spectrum of Py-TPE-COF (blue) shows a

–C=N– stretch at 1622 cm-1, indicating the successful formation of imine bonds.

S13

VII. Gas sorption data of Py-TPE-COF

Figure S11. Nitrogen adsorption (filled symbols) and desorption (empty symbols) isotherms of Py-TPE-COF,

surface area = 986.7 m2/g, total pore volume = 0.77 (P/P0 = 0.98)

S14

Figure S12. BET surface area plot for Py-TPE-COF calculated from the absorption isotherm.

S15

Figure S13. Pore size distribution of Py-TPE-COF calculated by NLDFT (slit pores model). The pore size is

1.1nm

S16

VIII. Photoluminescence image of Py-TPE-COF, model compounds, reference imine COFs

`

Figure S14. Photoluminescence image of a) COF materials Py-TPE-COF; c) TPE-M (4); d) Py-M (3); dispersed in

THF solution, using 365 nm illumination.

Figure S15. Photoluminescence image of Py-TPE-COF dispersed in a) THF; b) acetone; b) acetonitrile; c)

dimethylformamide solution, using 365 nm illumination.

Figure S16. Photoluminescence image of a) COF materials Py-TPE-COF; b) Py-COF; c) TPE-COF dispersed in

THF solution, using 365 nm illumination.

S17

Figure S17. Photoluminescence image of COF materials Py-TPE-COF dispersed in acetone solution, using 365 nm

illumination. Left: COF solutions before quenching experiments; Right: COF solutions after the addition of a) 0 ppm;

b) 3 ppm; c) 6 ppm; d) 9 ppm TNP.

S18

IX. UV-VIS spectra and PLQY data of Py-TPE-COF

Figure S18. Normalized UV spectra of model compounds (TPE-M, Py-M) and Py-TPE-COF dispersed in THF.

S19

Figure S19. Lifetime profile of the Py-TPE-COF: TCSPC traces (■), instrument response functions (□), and the

corresponding diexponential deconvolution fits (red lines). Photoexcitation was achieved with a picosecond diode

laser at 463 nm.

S20

Figure S20. Normalized FL emission spectra of Py-TPE-COF in different solvents, using 365 nm illumination.

S21

Figure S21. Fluorescence quenching of the Py-TPE-COF upon addition of TNP (0−25 ppm) in acetone, using 365

nm illumination.

S22

Figure S22. Stern−Volmer plot of the fluorescence quenching by TNP, the slope of linear fit is 3.13

S23

Figure S23. Degree of fluorescence intensity quenched (selectivity) upon addition of the nitro compounds (10

ppm, Py-TPE-COF dispersed in acetone, using 365 nm illumination).

S24

X. SEM and TEM image of Py-TPE-COF

Figure S24. SEM image of Py-TPE-COF. The image showed that Py-TPE-COF adopted a sheet-like morphology

with an average particle size of ca. 300 nm.

Figure S25. TEM image of Py-TPE-COF.

S25

XI. Structure Modelling of Py-TPE-COF5

Table S1 Fractional atomic coordinates for the unit cell of Py-TPE-COF with C2/m space group.

Space Group: monoclinic, C2/m

a = 42.6323, b = 43.7221, c = 4.5734

α=γ=90.0o, β=78.8o

Atom x y z

C1 0.47202 0.06528 0.46498

C2 0.47169 0.0327 0.48205

C3 0.44383 0.01599 0.49006

C4 0.42471 0.07573 0.19343

C5 0.44389 0.0838 0.40661

C6 0.43669 0.11045 0.5579

C7 0.41054 0.12801 0.50268

C8 0.39069 0.11887 0.29994

C9 0.39783 0.09264 0.14592

N10 0.36138 0.13376 0.27678

C11 0.35848 0.16298 0.23142

C12 0.32822 0.17794 0.2726

C13 0.3087 0.16889 0.48846

C14 0.28269 0.18635 0.56123

C15 0.27511 0.21322 0.41781

C16 0.29272 0.21964 0.18114

C17 0.31983 0.20319 0.11618

C18 0.02695 0.06497 0.56568

C19 0.02682 0.03253 0.57549

C20 0.0526 0.016 0.66331

C21 0.07985 0.0805 0.40852

C22 0.0553 0.08332 0.59855

C23 0.05624 0.10627 0.79692

C24 0.08127 0.12656 0.80208

C25 0.10551 0.12417 0.60698

C26 0.10468 0.1009 0.41224

N27 0.13025 0.14596 0.58777

C28 0.13918 0.16412 0.77992

C29 0.16565 0.1844 0.727

C30 0.19094 0.18342 0.89416

C31 0.21711 0.20124 0.83331

C32 0.2192 0.21888 0.5952

C33 0.19266 0.22172 0.44147

C34 0.16624 0.20425 0.5042

C35 0.24887 0.23419 0.50825

S26

H36 0.42159 0.02739 0.50066

H37 0.43021 0.05602 0.06671

H38 0.45095 0.11734 0.72311

H39 0.40488 0.14792 0.62681

H40 0.38256 0.08544 -0.01088

H41 0.37867 0.17698 0.18388

H42 0.31439 0.14931 0.61173

H43 0.26994 0.17879 0.73775

H44 0.33413 0.21013 -0.05613

H45 0.07294 0.02767 0.73457

H46 0.07913 0.0633 0.25072

H47 0.03723 0.10895 0.94323

H48 0.08078 0.14483 0.95052

H49 0.12289 0.09924 0.25781

H50 0.12984 0.16198 0.98504

H51 0.19064 0.16853 1.06955

H52 0.23549 0.20137 0.97478

H53 0.14642 0.20593 0.37712

H54 0.21427 0.26189 0.94832

H55 0.19222 0.2372 0.27127

C56 0 0.01629 0.5

C57 0 0.08067 0.5

C58 0 0.48361 0.5

C59 0 0.41911 0.5

H60 0 0.10562 0.5

H61 0.5 0.10572 0.5

S27

Figure S26. AA-stacking mode of Py-TPE-COF (Eclipsed structure, ten layers with perspective projection, view

from c axis. C, gray; H, white; N, blue), unit cell parameters: a = 42.63 Å, b = 43.72 Å, c = 4.57 Å, α = γ = 90°, β

=78.8° with C2/m space group

Figure S27. AA-stacking mode of Py-TPE-COF (Eclipsed structure, seven layers with perspective projection, view

from b axis. C, gray; H, white; N, blue) unit cell parameters: a = 42.63 Å, b = 43.72 Å, c = 4.57 Å, α = γ = 90°, β

=78.8° with C2/m space group

S28

Figure S28. AB-stacking mode of Py-TPE-COF (Staggered structure, ten layers with perspective projection, views

from c axis. C, gray; H, white; N, blue, lower layer, pink.), unit cell parameters: a = 42.63 Å, b = 43.72 Å, c = 9.15

Å, α = γ = 90°, β =78.8° with P1 space group

Figure S29. AB-stacking mode of Py-TPE-COF (Staggered structure, seven layers with perspective projection,

views from b axis. C, gray; H, white; N, blue) unit cell parameters: a = 42.63 Å, b = 43.72 Å, c = 9.15 Å, α = γ =

90°, β =78.8° with P1 space group

S29

XII. References:

1) S. Reuter, D. Bessinger, M. Döblinger, C. Hettstedt, K. Karaghiosoff, S. Herbert, P. Knochel, T. Clark,

and T. Bein. J. Am. Chem. Soc. 2016, 138, 16703.

2) L. Ascherl, T. Sick, J. T. Margraf, S. H. Lapidus, M. Calik, C. Hettstedt, K. Karaghiosoff, M.

Döblinger, T. Clark, K. W. Chapman, F. Auras and T. Bein, Nat. Chem. 2016, 8, 310.

3) H. Qu, Y. Wang, Z. Li, X. Wang, H. Fang, Z. Tian and X. Cao, J. Am. Chem. Soc., 2017, 139, 18142.

4) T.-Y. Zhou, S.-Q. Xu, Q. Wen, Z.-F. Pang and X. Zhao, J. Am. Chem. Soc. 2014, 136, 15885.

5) Dassault Systèmes BIOVIA, Materials Studio, Version 2016, San Diego: Dassault Systèmes, 2017