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Electronic
Supplementary
Information
(ESI)
An Imidazole-Functionalized Polyacetylene: Convenient Synthesis and
Selective Chemosensor for Metal Ions and Cyanide
Qi Zeng,a Ping Cai,a Zhen Li,*a Jingui Qina and Ben Zhong Tangb
a
Department of Chemistry, Hubei Key Lab on Organic and Polymeric Opto-Electronic Materials,
Wuhan University, Wuhan, 430072, China. Fax: 86 27 68756757; Tel: 86 27 62254108; E-mail:
[email protected].
b
Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay,
Kowloon, Hong Kong, China.
Materials and Instrumentations
N, N-Dimethylformamide (DMF) was dried over and distilled from CaH2 under an atmosphere
of
dry
nitrogen.
NaNO3,
KNO3,
Ba(NO3)2,
AgNO3,
Cr(NO3)3·9H2O,
Co(NO3)2·6H2O,
Ca(NO3)2·4H2O, Pb(NO3)2, Ni(NO3)2·6H2O, Zn(NO3)2·6H2O, Cu(NO3)2·3H2O, Al(NO3)3·9H2O,
Fe(NO3)3·9H2O, FeSO4·7H2O, 3CdSO4·8H2O, MnSO4·H2O, NaCl, KBr, KI, Na2SO4, K3PO4·3H2O,
Na2HPO4·12H2O, NaClO4, KCNS and NaF were of analytical grade, and purchased from Sinopharm
Chemical Reagent Beijing Co.,Ltd.
1
H-NMR spectroscopy study was conducted with a Varian Mercury300 spectrometer using
tetramethylsilane (TMS; δ = 0 ppm) as internal standard. Or 1H and 13C NMR spectra were measured
on a Bruker ARX 300 spectrometer using tetramethylsilane (TMS; δ = 0 ppm) as internal standard.
The Fourier transform infrared (FTIR) spectra were recorded on a PerkinElmer-2 spectrometer in the
region of 3000–400 cm-1. UV-visible spectra were obtained using a Shimadzu UV-2550 spectrometer.
Elementary analysis was taken on a Vario EL III elementary analysis instrument. Gel permeation
chromatography (GPC) was used to determine the molecular weights of polymers. GPC analysis was
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is (c)an
TheAgilent
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of Chemistry
performed
1100
series 2008
HPLC system and a G1362A refractive index detector.
Polystyrene standards were used as calibration standards for GPC. THF was used as an eluent and
the flow rate was 1.0 mL/min. Photoluminescence spectra were performed on a Hitachi F-4500
fluorescence spectrophotometer.
Scheme S1
(CH 2) 3Cl
WCl6/Ph4 Sn
C
60 oC, Toluene
S1
P0
C
n
(CH2 )3
Cl
Scheme 1
HN
C C n
(CH 2) 3
P0
Cl
N
, KOH
C C x C C y
n
(CH2 )3 (CH 2 )3
DMF
N
x = 0.36; Cl
y = 0.64.
N
P1
Synthesis and Characterization
Synthesis of (5-Chloro-pent-1-ynyl)-benzene (S1)
To a 250 mL flask were added 90 mg of copper (I) iodide, 180 mg of
dichlorobis(triphenylphosphine)palladium and 90 mg of triphenylphosphine, in the glove box.
Triethylamine (250 mL), 10.2 g of iodobenzene (50mmol) and 5.2 g of 5-chloro-1-pentyne (50mmol)
were then injected. The resultant mixture was stirred at room temperature overnight. The solid was
removed by filtration and the solvent was evaporated.
The crude product was purified on a silica
gel column using chloroform as eluent. Colorless oil of 1 was obtained in 89 % yield (7.9 g). 1H
NMR (300 MHz, CDCl3), δ (TMS, ppm): 7.41 (d, 2H), 7.28 (m, 3H), 3.70 (t, 2H), 2.60 (t, 2H), 2.04
(m, 2H).
13
C NMR (75 MHz, CDCl3), δ (TMS, ppm): 131.7, 128.5, 127.7, 123.7, 88.1, 81.4, 43.7,
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31.5,
16.9.
Synthesis of P0
Into a baked 80-mL Schlenk tube with a stopcock in the sidearm was added 1.14 g of monomer
S1. The tube was evacuated under vacuum and then flushed with dry nitrogen three times through
the side arm. Freshly distilled toluene (16 ml) was injected into the tube to dissolve the monomer.
The catalyst solution was prepared in another tube by dissolving 127.2 mg of tungsten (VI) chloride
and 137.6 mg of tetraphenyltin in 16 mL of toluene. The two tubes were aged at 60 oC for 15 min
and the monomer solution was transferred to the catalyst solution using a hypodermic syringe. The
reaction mixture was stirred at 60 oC for 24 hours.
The resultant solution was then cooled to room
temperature, diluted with 35 mL of chloroform, and added dropwise to 2500 mL of methanol
through a cotton filter under stirring.
The precipitate was allowed to stand overnight, which was
then filtered. The polymer was washed with methanol and dried in a vacuum oven to a constant
weight, shallow green powder (0.78 g, 68.4 %). Mw = 15700, Mw/Mn = 2.27. (GPC, polystyrene
calibration). IR (thin film), υ (cm-1): 3064 (Ar-H stretching), 2954, 2870 (CH2 stretching). 1H NMR
(300 MHz, CDCl3), δ (TMS, ppm): 0.8-2.6 (-CH2-), 2.6-3.4 (-CH2-), 6.5-7.8 (ArH). UV-Vis (Ethanol,
1.06×10-4 mol/L): λmax (nm): 302nm.
Synthesis of P1
P0 (89mg), imidazole (68 mg, 1.0 mmol), potassium hydroxide (140mg, 2.5mmol) were added
to dry DMF (10 mL). After stirred at 80 °C for 3 days, the resultant mixture was filtered, then the
filtrate was added to a dialyzer bag. The bag was immersed in distilled water (the water was changed
every two hours) for several day to remove small molecules, such as imidazole (which would enter
into water as its molecular weight is lower than 800). It was observed that some yellow precipitant
yielded in the bag during the dialyzing process. The yellow powder was collected, and dried in a
vacuum oven to a constant weight (47mg, 44.7%). 1H NMR (CH3OD) δ (ppm): 0.9-2.5 (-CH2-),
3
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Royal (ArH).
Society ofEA:
Chemistry
2008 C 73.09, H 6.620, N 9.015. UV-Vis (Ethanol, 1.06×10-4
2.5-4.4
(-CHis2-),
6.0-7.9
Found:
mol/L): λmax (nm): 302nm.
Preparation of Polymer Thin Films.
The polymers were dissolved in ethanol (concentration ~3 wt %) and the solutions were filtered
through syringe filters. Polymer films were spin-coated onto glass substrates, which were cleaned by
N, N-dimethyformide, acetone, distilled water and THF sequentially in ultrasonic bath before use.
Residual solvent was removed by heating the films in a vacuum oven at 40 oC.
Preparation of solutions.
Preparation of solutions of metal ions and anions
0.2 mmol of each inorganic salt (NaNO3, 17.0 mg; KNO3, 20.2 mg; Ba(NO3)2, 52.3 mg; AgNO3,
34.0 mg; Cr(NO3)3·9H2O, 80.0 mg; Co(NO3)2·6H2O, 58.2 mg; Ca(NO3)2·4H2O, 47.2 mg;
Ni(NO3)2·6H2O, 58.2 mg; Zn(NO3)2·6H2O, 59.5 mg; Cu(NO3)2·3H2O, 48.3 mg; Al(NO3)3·9H2O,
75.0 mg; Fe(NO3)3·9H2O, 80.8 mg; Pb(NO3)2, 66.2 mg; FeSO4·7H2O, 55.6 mg; 3CdSO4·8H2O, 51.3
mg; MnSO4·H2O, 33.8 mg; NaCl, 11.7 mg; KBr, 23.8 mg; KI, 33.2 mg; Na2SO4, 28.4 mg;
K3PO4·3H2O, 53.2 mg; Na2HPO4·12H2O, 71.6 mg; NaClO4, 24.4 mg; KCNS, 19.4 mg; NaF, 8.4 mg)
was dissolved in distilled water (10 mL) to afford 2×10-2 mol/L aqueous solution. The stock
solutions could be diluted to desired concentration with water when needed.
Preparation of polymer solutions
P1 (2.1 mg) was dissolved in ethanol to afford the stock solution with the concentration of
1.06×10-3 mol/L. This stock solution was diluted to 1.06×10-4 mol/L and 0.528×10-4 mol/L with
ethanol.
P0 (1.9 mg) was dissolved in the mixture solvent (10 mL) of ethanol and DMF (1:1) to afford
the stock solution with the concentration of 1.06×10-3 mol/L. And this stock solution (1 mL) was
diluted to 1.06×10-4 mol/L with ethanol.
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P0journal
(1.9 mg)
andRoyal
imidazole
mg)
were
dissolved in the mixture solvent (10 mL) of ethanol
and DMF (1:1) to afford the stock solution with the concentration of 1.06×10-3 mol/L. And this stock
solution (1 mL) was diluted to 1.06×10-4 mol/L with ethanol.
Calculation of x , y and molar molecular weight of P1
C C x C C y
n
(CH2)3 (CH 2 )3
Cl
x = 0.36;
y = 0.64.
N
N
P1
x, y was calculated according to the results of Elementary Analysis. EA: Found: C 73.09, H
6.620, N 9.015.
(2×14.01) y/(210.27 y+178.66 x)×100% = 9.015%
x = 0.36
x+y = 1
y = 0.64
Mw (per unit)=210.27×0.64+178.66×0.36=198.89
Fluorescence intensity changes of P1 with metal ions
A solution of P1 (1.06×10-4 mol/L) was prepared in ethanol. The solutions of metal ions (2×10-2
mol/L) were prepared in distilled water. A solution of P1 (3.0 mL) was placed in a quartz cell (10.0
mm width) and the Fluorescence spectrum was recorded. The ion solution was introduced (4 μL) and
fluorescence intensity changes were recorded at room temperature every time (Excitation
wavelength: 335 nm).
Fluorescence titration of P1 with metal ions
A solution of P1 (1.06×10-4 mol/L) was prepared in ethanol. The solutions of metal ions were
prepared in distilled water. A solution of P1 (3.0 mL) was placed in a quartz cell (10.0 mm width)
and the Fluorescence spectrum was recorded. The ion solution was introduced in portions and
fluorescence intensity changes were recorded at room temperature every time (Excitation
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wavelength:
335
nm).
Ions
C (mol/L)
Cu2+
5×10-4
2, 4, 6, 8, 10, 12, 16, 20, 24, 30, 40, 50, 60, 60+2a
Fe3+
5×10-4
2, 4, 6, 10, 14, 22, 30, 40, 50, 60, 60+1 a, 60+2 a, 60+3 a, 60+4 a, 60+5a
Fe2+
5×10-4
2, 4, 6, 8, 10, 16, 20, 24, 30, 40, 50, 60, 60+1 a, 60+2 a, 60+3 a, 60+4 a,60+5a
Co2+
5×10-4
2, 4, 6, 8, 10, 12, 16, 20, 24, 30, 40, 50, 60, 60+1 a, 60+2 a, 60+3 a, 60+4 a, 60+5a
Ni2+
2×10-3
2, 4, 6, 8, 10, 12, 16, 20, 30, 40, 50, 60, 60+1 a,60+2a
Cr3+
2×10-2
2, 4, 6, 8, 12, 16, 24, 32, 48
Al3+
2×10-2
2, 4, 12, 20, 30, 40, 50, 60
Pb2+
2×10-2
2, 4, 12, 20, 30, 40, 50, 60
a
Total volume (μL)
The concentration of the metal ions were changed to 2×10-2 mol/L.
Fluorescence intensity changes of P1 by Cu2+ in the presence of other metal ions
Fluorescence intensity changes were recorded after additions of 4 μL of the solutions of metal
ions (Na+, K+, Ca2+ , Ba2+, Co2+, Fe3+, Fe2+, Mn2+ , Ni2+, Cr2+, Ag2+ , Zn2+ , Cd2+, Al2+ and Pb2+; the
concentration of the metal ions were 2×10-2 mol/L) to the solution of P1. Then 4 μL of the solution
of Cu2+ (2×10-2 mol/L) was added and fluorescence intensity changes were recorded (Excitation
wavelength: 335 nm).
Fluorescence intensity changes of the mixture of P0 and imidazole with metal ions
A solution of the mixture of P0 and imidazole (1.06×10-4 mol/L) was prepared in ethanol. The
solutions of metal ions (2×10-2 mol/L) were prepared in distilled water. A solution of the mixture of
P0 and imidazole (3.0 mL) was placed in a quartz cell (10.0 mm width) and the Fluorescence
spectrum was recorded. The ion solution was introduced (4 μL) and fluorescence intensity changes
were recorded at room temperature every time (Excitation wavelength: 335 nm).
Fluorescence intensity changes of P1+ Cu2+ with CN6
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A solution
(0.528×10
mol/L)
was prepared
in ethanol. The solutions of NaCN (1×10-2
mol/L) was prepared in distilled water. A solution of P1 (3.0 mL) was placed in a quartz cell (10.0
mm width) and the Fluorescence spectrum was recorded. The solution of Cu2+ (5×10-4 mol/L, 40 μL)
was added to quench the Fluorescence. Then NaCN solution was introduced in portions (total
volume: 20, 28, 36, 44, 52, 60 μL) and fluorescence intensity changes were recorded at room
temperature every time (Excitation wavelength: 335 nm).
Fluorescence intensity changes of P1+ Cu2+ with other anions
A solution of P1 (0.528×10-4 mol/L) was prepared in ethanol. The solutions of anions (2×10-2
mol/L) were prepared in distilled water. A solution of P1 (3.0 mL) was placed in a quartz cell (10.0
mm width) and the Fluorescence spectrum was recorded. The ion solution was introduced (10 μL)
and fluorescence intensity changes were recorded at room temperature every time (Excitation
wavelength: 335 nm).
Fluorescence “turn off-turn on” of polymer film by ammonia
Fluorescence intensity change was recorded after the film of P1 immersed in aqueous Cu(NO3)2
solution (2×10-2 mol/L). Then the film was immersed in ammonia aqueous solution and fluorescence
intensity change was recorded at room temperature (Excitation wavelength: 335 nm).
Fluorescence “turn off-turn on” of polymer film by CNFluorescence intensity change was recorded after the film of P1 immersed in aqueous Cu(NO3)2
solution (2×10-2 mol/L). Then the film was immersed in NaCN aqueous solution (1.4×10-3 or
1.0×10-2 mol/L) and fluorescence intensity changes were recorded at room temperature each time
(Excitation wavelength: 335 nm).
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Normalized Emission Intensity
100
P1
2+
P1+Zn
+
P1+Ag
+
P1+K
2+
P1+Mn
2+
P1+Ca
2+
P1+Cd
+
P1+Na
2+
P1+Ba
2+
P1+Pb
3+
P1+Al
3+
P1+Cr
2+
P1+Ni
2+
P1+Fe
3+
P1+Fe
2+
P1+Co
2+
P1+Cu
80
60
40
20
0
360
420
480
540
600
660
Wavelength (nm)
Figure S1. Emission quenching of the solution of P1 in ethanol by different metal ions. The polymer
concentration is fixed at 1.06×10-4 mol/L, and the concentrations of all metal ions are the same
(2.67×10-5 mol/L), or in ppm (from Zn2+ to Cu2+): 1.74, 2.88, 1.04, 1.47, 1.07, 3.00, 0.61, 3.66, 5.53,
0.72, 1.39, 1.57, 1.49, 1.49, 1.57, 1.70. Excitation wavelength (nm): 335.
3200
CCu (ppm)
2800
2+
0.00
0.02
0.04
0.06
0.08
0.11
0.13
0.17
0.21
0.25
0.32
0.42
0.53
0.64
1.48
Intensity (au)
2400
2000
1600
1200
800
400
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S2. Emission quenching of the solution of P1 in ethanol by Cu2+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
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3200
CFe (ppm)
3+
2800
0.00
0.02
0.04
0.06
0.10
0.13
0.21
0.28
0.37
0.47
0.56
0.93
1.30
1.68
2.05
2.42
Intensity (au)
2400
2000
1600
1200
800
400
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S3. Emission quenching of the solution of P1 in ethanol by Fe3+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
3200
CFe (ppm)
2+
2800
0.00
0.02
0.04
0.06
0.07
0.09
0.15
0.19
0.22
0.28
0.37
0.47
0.56
0.93
1.30
1.68
2.05
2.42
Intensity (au)
2400
2000
1600
1200
800
400
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S4. Emission quenching of the solution of P1 in ethanol by Fe2+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
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3200
CCo (ppm)
2+
2800
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.16
0.20
0.24
0.30
0.39
0.49
0.59
0.98
1.38
1.77
2.16
Intensity (au)
2400
2000
1600
1200
800
400
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S5. Emission quenching of the solution of P1 in ethanol by Co2+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
3200
CNi (ppm)
2+
Intensity (au)
2800
0.00
0.08
0.16
0.24
0.31
0.39
0.47
0.63
0.78
1.17
1.57
1.96
2.35
2.74
3.13
2400
2000
1600
1200
800
400
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S6. Emission quenching of the solution of P1 in ethanol by Ni2+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
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3200
CCr (ppm)
2800
3+
0.00
0.69
1.39
2.08
2.77
4.16
5.55
8.32
11.09
16.64
Intensity (au)
2400
2000
1600
1200
800
400
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S7. Emission quenching of the solution of P1 in ethanol by Cr3+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
3000
Intensity (au)
2400
CAl (ppm)
3+
0
0.36
0.72
2.16
3.60
5.40
7.20
8.99
10.79
1800
1200
600
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S8. Emission quenching of the solution of P1 in ethanol by Al3+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
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3200
CPb (ppm)
2+
2800
0.00
2.76
5.53
16.58
27.63
41.44
55.25
69.07
82.88
Intensity (au)
2400
2000
1600
1200
800
400
0
350
400
450
500
550
600
650
Wavelength (nm)
Figure S9. Emission quenching of the solution of P1 in ethanol by Pb2+. Concentration: 1.06×10-4
mol/L. Excitation wavelength (nm): 335.
4000
P0+Imidazole
+
P0+Imidazole+K
2+
P0+Imidazole+Ca
+
P0+Imidazole+Na
2+
P0+Imidazole+Zn
2+
P0+Imidazole+Ba
2+
P0+Imidazole+Cu
2+
P0+Imidazole+Cd
2+
P0+Imidazole+Mn
+
P0+Imidazole+Ag
2+
P0+Imidazole+Ni
2+
P0+Imidazole+Pb
3+
P0+Imidazole+Al
2+
P0+Imidazole+Co
3+
P0+Imidazole+Cr
3+
P0+Imidazole+Fe
2+
P0+Imidazole+Fe
Intensity(au)
3000
2000
1000
0
360
400
440
480
520
560
600
640
Wavelength(nm)
Figure S10. Emission quenching of the solution of the mixture of P0 and Imidazole in ethanol by
different metal ions. The polymer concentration is fixed at 1.06×10-4 mol/L, and the concentrations
of all metal ions are the same (2.67×10-5 mol/L), or in ppm (from K+ to Fe2+): 1.04, 1.07, 0.61, 1.74,
3.66, 1.70, 3.00, 1.47, 2.88, 1.57, 5.53, 0.72, 1.57, 1.39, 1.49, 1.49. Excitation wavelength (nm): 335.
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302 nm
302 nm
(b)
453 nm
(C)
1.0
467 nm
466 nm
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0.0
0.0
Normalized PL intensity
Normalized absorption
323 nm
(a)
1.0
280 370 460 550 640 280 370 460 550 640 280 370 460 550 640
Wavelength (nm)
Figure S11.The UV-vis absorption and fluorescence spectra of P1 (a), the mixture of P0 and
imidazole (b) and P0 (c) in ethanol. The polymer concentration is 1.06×10-4 mol/L. Excitation
wavelength (nm): 335.
4000
P1
3000
PL Intensity (au)
2+
P1 + Cu + ammonia
2000
1000
2+
P1 + Cu
0
370
410
450
490
530
570
610
650
Wavelength (nm)
Figure S12. Fluorescence emission spectra P1 in solid states on a glass plate before immersion in
Cu2+ aqueous solution, after immersion in Cu2+ aqueous solution, and after immersion in ammonia
aqueous solution.
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Equation S1: the reaction between Cu2+ and CN2Cu2+ + 4CN- = 2CuCN + (CN)2 (CuCN is white precipitant).
Equation S2: the reaction between CuCN and CNCuCN + (x-1)CN- = [Cu(CN)x]1-x, (x = 2, 3, or 4, and generally 2 and 4.)
The stability constants (K), [Cu(CN)2]-: K = 1.00 ×1024; [Cu(CN)4]3-: K = 2.00 ×1030.
P1
1200
2+
-
PL Intensity (au)
P1 + Cu + CN (mol/L)
900
-4
2.0X10
-4
1.7X10
-4
1.5X10
-4
1.2X10
-5
9.0X10
-5
7.0X10
600
300
2+
P1 + Cu
0
350
410
470
530
590
650
Wavelength (nm)
Figure S13. Fluorescence emission spectra P1 in ethanol before added Cu2+, after added Cu2+, and
turned on by CN-. The polymer concentration is fixed at 0.528×10-4 mol/L. Excitation wavelength
(nm): 335.
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800
-
CN
2HPO4
3-
PO4
600
PL Intensity (au)
2-
SO4
-
2+
F
Cl
Br
ClO4
P1 + Cu + anions
400
-
weak luminescence
I
control
SCN
nonluminescence
200
0
350
410
470
530
590
650
Wavelength (nm)
Figure S14. Fluorescence emission spectra P1 in ethanol after added Cu2+, and turned on by CNand other anions. The polymer concentration is fixed at 0.528×10-4 mol/L, and concentration of all
anions is 7.0 × 10-5 mol/L. Excitation wavelength (nm): 335.
1200
P1
PL Intensity (au)
1000
800
600
2+
-
P1 + Cu + CN
400
200
2+
P1 + Cu
0
370
410
450
490
530
570
610
650
Wavelength (nm)
Figure S15. Fluorescence emission spectra P1 in solid states on a glass plate before immersion in
Cu2+ aqueous solution, after immersion in Cu2+ aqueous solution, and after immersion in sodium
cyanide aqueous solution (1.4×10-3 mol/L).
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1200
P1
PL Intensity (au)
900
2+
-
P1 + Cu + CN
600
300
2+
P1 + Cu
0
370
410
450
490
530
570
610
650
Wavelength (nm)
Figure S16. Fluorescence emission spectra P1 in solid states on a glass plate before immersion in
Cu2+ aqueous solutions, after immersion in Cu2+ aqueous solutions, and after immersion in sodium
cyanide aqueous solutions(1.0×10-2 mol/L).
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