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Electronic Supporting Information
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For
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A novel colorimetric and fluorescent sensor for fluoride detection based on a
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three-arm phenanthroline derivative
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Chaolong Yang,*1,2 Jing Xu,2,3 Wen Chen,1 Mangeng Lu, *2 Youbing Li, 1 Xuanlun
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Wang1
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Chongqing 400054, PR China
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2
School of Materials Science and Engineering, Chongqing University of Technology,
Key Laboratory of Polymer Materials for Electronics, Guangzhou Institute of
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Chemistry, Chinese Academy of Sciences, Guangzhou 510650, PR China
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-Azaaoba 6-3, Aoba-ku, Sendai, Japan
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki
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*Corresponding author E-mail: yclzjun@163.com; yclly2013@cqut.edu.cn (CL
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Yang), mglu@gic.ac.cn (MG Lu)
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Table of Contents:
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1. Synthetic procedures and characterization.
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2. Additional Tables (Table S1, S2) and Figures (Figure S1-S3).
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3. Determination of the detection of limit (LOD)
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Scheme S1 Synthetic procedure of desired receptor trisphen.
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1. Synthetic procedures and characterization.
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Synthesis of 1, 3, 5-tris(bromomethyl)- 2, 4, 6-trimethylbenzene
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1, 3, 5-tris(bromomethyl)- 2, 4, 6-trimethylbenzene was prepared according to the
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procedure described in the literature with some modification [1]. Mesitylene (12 g,
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100 mmol), paraformaldehyde (10.26 g, 340 mmol) and 75 ml of glacial acetic acid
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was rapidly added to a 150 ml three neck round bottom flask with 75 ml of HBr/acetic
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acid solution during magic stirring. The mixture solution was heated to 95 oC and kept
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at this temperature for 8 h, then poured into 200 ml of water to give amounts of white
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solid. The product from filtering was washed with 200 ml of anhydrous ethanol, and
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then was filtered and dried overnight at 60 oC to give 33.5 g of title compound, yield
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85%, mp 183-186 oC. FT-IR (KBr) (cm-1): 785, 1446.1, 2922. 1H NMR (400 MHz,
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CDCl3): δ 2.44 (s, 9H, Ar-CH3), 4.56(s, 6H,-CH2Br).
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δ12.1, 27.5, 134.7, 137.1.
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Synthesis of 1,10-phenanthroline-5,6-Dione.
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1,10-phenanthroline-5,6-dione was synthesized according to a modified literature
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procedure [2]. 1,10-phenanthroline monohydrate (10.16g, 51.3 mmol) and KBr (24.94
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g, 209.6 mmol) were added in a 250 ml three-neck round-bottom flask with a reflux
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condenser, mixture acid of 75 ml concentrated sulfuric acid and 35 ml concentrated
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C NMR (100 MHz, CDCl3):
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nitric acid was added rapidly during stirring, after the mixture acid finished, solution
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was heated to 125 oC and kept at this temperature for 3 h. After 3 h, heating
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temperature was reduced to 100 oC, and the reflux condenser was removed to allow
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bromine vapors escape from the reaction flask, and used the 10 M NaOH solution
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absorbed the bromine. After being cooled, the mixture was poured into 275 g ice and
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carefully neutralized to pH = 7 with 5 M sodium hydroxide solution, and cooled to
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room temperature. Then the yellow turbid solution was filtered, and residual solid was
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washed four times with 30 ml boiling water every time, and the filtrate was collected.
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The combined aqueous solution was extracted with 200 ml dichloromethane, dried
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over anhydrous magnesium sulfate, and evaporated under reduced pressure to give
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light-yellow solid. The crude product was recrystallized from 250 ml of toluene to
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give the yellow needle crystalline. The pure product was dried overnight in vacuum at
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60 oC, yield 80%. Mp: 253-256 oC. FT-IR (KBr) /cm-1: 3062, 1685, 1576, 1561,
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1460, 1414, 1314, 1292, 1205, 1115, 1009, 924, 808, 738.
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CDCl3), δ: 7.58(d, 16 Hz, 2H), 8.50(dd, 8 Hz, 2H), 9.11(dd, 8 Hz, 2H).
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1,3,5-Tris(4-formylphenoxymethyl)-2,4,6-trimethylbenzene.
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4-hydroxybenzaldehyde (4.2 g, 40 mmol), 1,3,5-tris(2-bromomethyl)-2,4,6-trimethyl-
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benzene (4.0 g, 10 mmol), and potassium carbonate (5.52 g, 20 mmol) were dissolved
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in 100 ml DMF, and reacted at 90 oC for 24 h. The resulting solution was poured into
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600 ml water, then filtered to get white solid, washed with large portion of water and
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ethanol, then the resulting solid was recrystallized from a mixture of acetic ether to
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give fine white crystals (4.88 g, 93%). 1H NMR (CDCl3, 400 MHz, ppm): 2.47 (9H, s,
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3×CH3), 5.22 (6H, s, 3× CH2), 7.13 (6H, d, aromatic), 7.89 (6H, d, aromatic), 9.93
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(3H, s, 3×CHO);13 C NMR (CDCl3 , 100 MHz, ppm): 16.42 (CH3), 65.67 (CH2),
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115.28, 132.48 (aromatic), 130.75, 131.68, 140.16, 164.34 (quaternary aromatic),
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191.11 (CHO); MS (ESI) m/z = 523.3 (M+H) + . FT-IR (KBr) υ(C=O) 1691 cm-1 .
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H NMR (400 MHz
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References
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[1] AW van der Made and RH van der Made. A convenient procedure for
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bromomethylation
of
aromatic
compounds.
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Selective
mono-,
bis-,
or
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trisbromomethylation. J Org Chem 1993; 58: 1262-1263.
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[2]
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and .LAMBDA.-[Ru(phen)2DPPZ]2+. J Am Chem Soc 1993; 115: 3448-3454.
Hiort
C,
Lincoln
P
and
Norden
B.
DNA binding
of
.DELTA.-
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2. Additional Figures (Figure S1-S4).
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Figure S1 UV-Vis absorption spectra of receptor trisphen (1×10-5 M) upon addition of
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different anions (3×10-5 M of F-, CH3COO-, H2PO4-, Cl-, Br-, I-, HSO4- and NO3-) in
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DMSO.
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Figure S2 Fluorescent emission spectra of trisphen in the presence of different
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concentrations (0-2.1×10-3 M) of AcO- ion in DMSO solution.
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Figure S3 The emission spectra changes of 5×10-4 M AcO- bonded trisphen with the
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addition of 5 and 10% water (ethanol).
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Figure S4 The changes of 1HNMR spectra for trisphen upon the addition of differen
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concentration AcO-.
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3. Determination of the detection of limit (LOD)
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The LOD of receptor trisphen was determined from the following equation:
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LOD = K*SD/S
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Where K = 3; SD is the standard deviation of the blank solution; S is the slope of the
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calibration curve.
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Figure S5 A plot of (A0-A ) vs F- concentrations at 321 nm.
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Y=A+B*X
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Parameter
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------------------------------------------------------------
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A
-0.00201
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B
612.9
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------------------------------------------------------------
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R
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------------------------------------------------------------
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0.99589 0.00102 5
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------------------------------------------------------------
SD N
Value
Error
0.00107
32.18794
P
3.1629E-4
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Figure S6 A plot of (A0-A ) vs AcO- concentrations at 321 nm.
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Y=A+B*X
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Parameter
Value
Error
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------------------------------------------------------------
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A
0.00201 3.77688E-4
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B
553.8
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11.38771
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R
SD N
P
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------------------------------------------------------------
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0.99937 3.60111E-4 5
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------------------------------------------------------------
<0.0001
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