Electronic Supplementary Material Supplementary Figures S1 ...
Electronic Supplementary Information Highly ... · Electronic Supplementary Information Highly...
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.
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)
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