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Electronic supplementary information (ESI)
One Novel Nitrogen Heterocyclic Ligand-based MOFs:
Synthesis, Characterization and Photocatalytic Properties
Qigao Shanga, Tianyu Zenga, Ke Gaoa, Nannan Liua, Qingrong Chenga,*,
Guiying Liaob, Zhiquan Pana, Hong Zhoua
Key Laboratory for Green Chemical Process of Ministry of Education,
Wuhan Institute of Technology, Wuhan 430073, P. R. China
Engineering Research Center of Nano-Geo Materials of Ministry of
Education, China University of Geosciences, Wuhan 430074, P. R. China.
Corresponding authors:
*(Q.C.) E-mail: [email protected]
Total number of pages: 11
Total number of Tables: 2
Total number of Figures: 4
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
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Synthesis
Synthesis of 1,3,5-tris(bromomethyl) benzene, A
Br
Br
Br
N
N
N
N
NN
BPO, benzene80°C , 2 h
Imidazole, KOH, acetonitrile
25°C , 0.5h
A B
Scheme 1. Synthesis of ligand 1,3,5-tris(imidazole-1-yl-methyl) benzene.
A mixture of the 1,3,5-Trimethylbenzen (24.18 g, 0.200 mol),
nbromosuccinimide (NBS,109.1 g, 0.611 mol) and benzoyl peroxide (BPO, 1.071 g,
0.044 mol) in dry Benzene (600 mL) was heated at 80 ℃ for 2 h, cooled to room
temperature and filtered. The solvent was washed with water (3 × 100 mL), saturated
saline (100 mL) and dried over anhydrous Na2SO4. The concentration under reduced
pressure was recrystallized with n-hexane: ethanol (1:1) to get colourless needle-like
crystals. Yield: 92%.
Synthesis of 1,3,5-tris(imidazole-1-yl-methyl) benzene, B
A mixture of the imidazole (2.040 g, 0.029 mol) and KOH (3.000 g, 0.053
mol) in dry acetonitrile (50 mL), was stirred vigorously at 25 ℃ for 0.5 h. Then 1,3,5-
tris (bromomethyl) benzene (3.570 g, 0.010 mol) in acetonitrile (30 mL) was added to
the reaction mixture slowly and stirred for 30 min at 25 ℃. The reaction mixture was
filtered and the solvent was condensed under reduced pressure, the crude product was
washed with trichloromethane (3 × 50 mL) and filtered. The organic phase was
concentrated under reduced pressure and recrystallized with acetone and chloroform
to form colourless needle-like crystals. Yield: 88.0%.M.P.:155-158℃. Anal.Calcd for
C18H18N6(%):C, 67.90; H, 5.70; N, 26.40. Found(%): C, 67.85; H, 5.72; N, 26.43. As
Figure s1 shown is the FTIR spectra of TIB. IR (cm-1, KBr pellets): 3383w, 3103w,
3075w, 2933w, 1665m, 1501s, 1437s, 1388m, 1343w, 1274s, 1106m, 1076s, 1031s,
987 w.
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Physical Measurements.The crystal data were collected were collected on a Bruker SMART APEX CCD
diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) using
the SMART and SAINT programs. The structure was processed by direct methods
and refined on F2 by full-matrix least-squares methods with SHELXTL version 5.1.
Nonhydrogen atoms of the ligand backbones were refined anisotropically. All the
hydrogen atoms of the TIB backbones were fixed geometrically at calculated
positions and allowed to ride on the parent non-hydrogen atoms. FT-IR spectra (KBr
pellets) were recorded on a Perkin−Elmer GX FTIR spectrometer in the region
4000−450 cm −1. CHN analyses were done using elementar vario MICRO CUBE
analyzer. UV−vis diffuse reflectance spectra (DRS) were tested on a PerkinElmer
Lambda2S spectrophotometer, in the range of 200−800 nm in the solid state. The
UV−vis spectra for MB solution were measured on a Shimadzu UV 2450
spectrometer (UV-3600, Shimadzu, Japan). Thermogravimetric analysis (TGA) test
were recorded on TG-DTA 2010S MAC apparatus under N2 atmosphere in the
temperature range 40−900 °C with a heating rate of 10 °C min-1. Powder X-ray
diffraction (PXRD) patterns were collected using a PANalytical Empyrean (PIXcel
3D detector) system with CuKα radiation (λ= 0.15418 nm), and the 2θ range of 5−80°.
The X-ray photoelectron spectra (XPS) were recorded on an ESCALAB250
spectrometer (Thermo-VG Scientific) using MgKα radiation (1253.6 eV) and the
binding energy values were calibrated with respect to the C (1s) peak (284.6 eV).
Photocatalytic experiments: 300 W ceramic metal halide lamp (PerkinElmer) with
420 nm optical filter. Liquid chromatography-Mass spectroscopy (LC-MS) analysis
was performed in Thermo Scientific Q Exactive orbitrap instrument. The column used
was Waters Acquity UPLC BEH C18 with dimensions of 1.7 um 201m X 50 mm. The
electron spin resonance (ESR) spectra were detected using a Bruker EPR A 300-10/12
spectrometer to measure the activated species.
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Figure S1. FTIR spectra of TIB.
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Table S1. Crystallographic data for complex 1.
Complex 1
formula C36H36CoN12O4S
CCDC deposit no 1882339
Formula weight 791.76
Crystal system hexagonal
Space group P 63(173)
a (Å) 19.6072(6)
b (Å) 19.6072(6)
c (Å) 24.0094(13)
α (deg) 90
β (deg) 90
γ (deg) 120
V(Å3) 7993.6(7)
Z 8
Dcalcd(g cm-3) 1.31572
F(000) 3288.0
H,k,l max 23,23,28
Mu(Mo-Ka)[mm-1] 0.535
Temp , k 173
Nref,Npar 8741,718
R1 ,wR1 0.0685,0.1943
S 1.089
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Table S2. Selected bond distances (A°) and angles (º) for complex 1.Complex 1
bond lengths (Å) bond angles (o) bond angles (o)
Co1-N15 2.141(9) N15-Co1-N13 92.4(3) N3-Co1-N5 94.0(3)
Co1-N13 2.155(9) N15-Co1-N3 87.1(3) N1-Co1-N5 86.4(4)
Co1-N3 2.157(9) N13-Co1-N3 86.8(3) N15-Co1-N9 86.8(3)
Co1-N1 2.168(10) N15Co1-N1 92.5(3) N13-Co1-N9 177.0(4)
Co1-N5 2.168(9) N13-Co1-N1 94.2(4) N3-Co1-N9 90.3(3)
Co1-N9 2.168(9) N3-Co1-N1 178.9(3) N1-Co1-N9 88.7(4)
Co2-N11 2.188(8) N15-Co1-N5 178.9(4) N5-Co1-N9 93.4(3)
Co2-N7 2.178(8) N13-Co1-N5 87.4(3) N7-Co2-N11 177.1(3)
N7-Co2-N7 93.7(3) N11-Co2-N11 92.5(3)
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Figure S2. FTIR spectra of complex 1.
Figure S3. TGA, DSC and DTG curves of complex 1.
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Figure S4. Tandem mass spectrum of methylene blue intermediate degradation product ions m/z=270 (a), m/z=280 (b), m/z=279 (c), m/z=294 (d), m/z= 295 (e), m/z=352 (f) and m/z=288 (f)
