Organosilica Hybrid MaterialsTable S1 Relative Ln3+ contents for the PMO@Eu,Tb, PMO@Eu,Tb_phen and...
Transcript of Organosilica Hybrid MaterialsTable S1 Relative Ln3+ contents for the PMO@Eu,Tb, PMO@Eu,Tb_phen and...
SUPPORTING INFORMATION
Chemical Sensors Based on Nano-Sized Lanthanide-Grafted Periodic Mesoporous
Organosilica Hybrid Materials
Anna M. Kaczmarek,* and Pascal Van Der Voort*
COMOC – Center for Ordered Materials Organometallics and Catalysis, Department of Chemistry, Ghent
University, Krijgslaan 281-S3, B-9000 Ghent, Belgium
Table S1 Relative Ln3+ contents for the PMO@Eu,Tb, PMO@Eu,Tb_phen and PMO@Eu,Tb_bpy samples from synthesis (calcd.) and as determined by XRF.
Sample Molar amounts used in
synthesis [mmol]
Eu3+ ion Tb3+ ion
Eu3+ Tb3+ Calcd. XRF Calcd. XRF
PMO@Eu,Tb 0.50 0.50 50% 48.7% 50% 51.3%
PMO@Eu,Tb_phen 0.50 0.50 50% 49.8% 50% 50.1%
PMO@Eu,Tb_bpy 0.50 0.50 50% 50.6% 50% 49.4%
Figure S1 1H NMR of the PMO precursor (CDCl3, 300 MHz).
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Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2019
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excitation emission
Inte
nsity
(a.u
.)
Wavelength (nm)
Figure S2 RT combined excitation-emission spectrum of the pristine PMO (the dotted line represents the excitation spectrum and the continuous line represents the emission spectrum).
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Inte
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(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
d e
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
Figure S3 Left: RT solid-state combined excitation-emission spectrum of PMO@Tb, right: RT combined excitation-emission spectrum of PMO@Tb in water suspension. The emission spectra were recorded when exciting into the maximum of the broad ligand band and the excitation spectra were monitored at the 5D4→7F5 transition peak.
Table S2 Assignment of peaks labeled in Figure S3 (PMO@Tb in solid-state).Label Wavelength (nm) Transitions
Excitationa 295 π→π*
Emissionb 488 5D4→7F6
c 542 5D4→7F5
d 581 5D4→7F4
e 619 5D4→7F3
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b cd e
f
g
h
i
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
Figure S4 Left: RT solid-state combined excitation-emission spectrum of PMO@Eu, right: RT combined excitation-emission spectrum of PMO@Eu in water suspension. The emission spectra were recorded when exciting into the maximum of the broad ligand band and the excitation spectra were monitored at the 5D0→7F2 transition peak.
Table S3 Assignment of peaks labeled in Figure S4 (PMO@Eu in solid-state).Label Wavelength (nm) Transitions
Excitationa 293 π→π*b 361 5D4←7F0
c 392 5L6←7F0
d 462 5D2←7F0
Emissione 578 5D0→7F0
f 591 5D0→7F1
g 611 5D0→7F2
h 651 5D0→7F3
i 700 5D0→7F4
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0 2 4 6 8
Inte
nsity
(a.u
.)
Time (ms)
PMO@Tb solid decay fit Model ExpDec2
Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr
1991.58719
Adj. R-Square 0.99964Value Standard Error
y0 39.9342 2.49984A1 8785.80773 147.8543t1 1.00449E6 8273.83916A2 7118.97697 126.88517t2 350243.01176 6431.61163
0 1 2 3 4
Inte
nsity
(a.u
.)
Time (ms)
PMO@Tb susp. decay fit
Model ExpDec1Equation y = A1*exp(-x/t1) + y0
Reduced Chi-Sqr
598.52151
Adj. R-Square 0.99846Value Standard Error
y0 24.72018 0.94972
A1 2881.71989 2.28883
t1 879583.97549 1453.48678
Figure S5 Left: decay profile of PMO@Tb sample in solid-state form, right: decay profile of PMO@Tb sample in suspension. The decay times were recorded when exciting into the maximum of the broad ligand band and monitoring at the 5D4→7F5 transition peak.
0 1 2 3 4
Inte
nsity
(a.u
.)
Time (ms)
PMO@Eu solid decay fit
Model ExpDec2Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr
974.71178
Adj. R-Square 0.99961Value Standard Error
y0 6.29781 1.82746A1 4172.54279 401.11486t1 459219.68072 13858.66879A2 11427.19659 358.00019t2 223648.31689 4351.61966
0 2 4 6 8In
tens
ity (a
.u.)
Time (ms)
PMO@Eu susp. decay fit
Model ExpDec2Equation y = A1*exp(-x/t1) +
A2*exp(-x/t2) + y0
Reduced Chi-Sqr 892.17106
Adj. R-Square 0.99985Value Standard Error
y0 6.09571 0.93535
A1 1944.43328 21.05273
t1 1.22605E6 9286.32875
A2 25114.2934 17.05928
t2 296586.21367 382.33662
Figure S6 Left: decay profile of PMO@Eu sample in solid-state form, right: decay profile of PMO@Eu sample in suspension. The decay times were recorded when exciting into the maximum of the broad ligand band and monitoring at the 5D0→7F2 transition peak.
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
de
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
de
Figure S7 Left: RT solid-state combined excitation-emission spectrum of PMO@Tb_phen, right: RT combined excitation-emission spectrum of PMO@Tb_phen in water suspension. The emission spectra were recorded when exciting into the maximum of the broad ligand band and the excitation spectra were monitored at the 5D4→7F5 transition peak.
Table S4 Assignment of peaks labeled in Figure S7 (PMO@Tb_phen in solid-state).Label Wavelength (nm) Transitions
Excitationa 312 π→π*
Emissionb 487 5D4→7F6
c 543 5D4→7F5
d 583 5D4→7F4
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e 620 5D4→7F3
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
d
e
f
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Inte
nsity
(a.u
.)Wavelength (nm)
excitation emission
Figure S8 Left: RT solid-state combined excitation-emission spectrum of PMO@Eu_phen, right: RT combined excitation-emission spectrum of PMO@Eu_phen in water suspension. The emission spectra were recorded when exciting into the maximum of the broad ligand band and the excitation spectra were monitored at the 5D0→7F2 transition peak. Table S5 Assignment of peaks labeled in Figure S8 (PMO@Eu_phen in solid-state).
Label Wavelength (nm) TransitionsExcitation
a 294 π→π*b 361 5D4←7F0
c 392 5L6←7F0
d 462 5D2←7F0
Emissione 578 5D0→7F0
f 591 5D0→7F1
g 610 5D0→7F2
h 650 5D0→7F3
i 701 5D0→7F4
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
d e
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
Figure S9 Left: RT solid-state combined excitation-emission spectrum of PMO@Tb_bpy, right: RT combined excitation-emission spectrum of PMO@Tb_bpy in water suspension. The emission spectra were recorded when exciting into the maximum of the broad ligand band and the excitation spectra were monitored at the 5D4→7F5 transition peak.
Table S6 Assignment of peaks labeled in Figure S9 (PMO@Tb_bpy in solid-state).Label Wavelength (nm) Transitions
Excitationa 322 π→π*
Emissionb 489 5D4→7F6
c 543 5D4→7F5
d 583 5D4→7F4
e 620 5D4→7F3
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emisison
a
b
c d
e
f
g
h
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
Figure S10 Left: RT solid-state combined excitation-emission spectrum of PMO@Eu_bpy, right: RT combined excitation-emission spectrum of PMO@Eu_bpy in water suspension. The emission spectra were recorded when exciting into the maximum of the broad ligand band and the excitation spectra were monitored at the 5D0→7F2 transition peak.
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Table S7 Assignment of peaks labeled in Figure S10 (PMO@Eu_bpy in solid-state).Label Wavelength (nm) Transitions
Excitationa 354 π→π*b 393 5L6←7F0
c 462 5D2←7F0
Emissiond 579 5D0→7F0
e 591 5D0→7F1
f 612 5D0→7F2
g 649 5D0→7F3
h 698 5D0→7F4
0 2 4 6 8
Inte
nsity
(a.u
.)
Time (ms)
Decay PMO@Tb_phen solid decay fit Model ExpDec2
Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr
19759.30571
Adj. R-Square 0.9993Value Standard Error
Decay3 y0 82.70967 6.15253Decay3 A1 26355.84301 279.32958Decay3 t1 350154.42972 2398.68917Decay3 A2 205971.16996 2720.95189Decay3 t2 61760.25845 513.10077
0 2 4 6 8
Inte
nsity
(a.u
.)
Time (ms)
Decay PMO@Tb_phen suspension decay fit
Model ExpDec2Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr 1386.6406
Adj. R-Square 0.99957Value Standard Error
Decay blank solution y0 24.21144 1.34546
Decay blank solution A1 10594.36328 48.32454
Decay blank solution t1 158785.77361 1464.13453
Decay blank solution A2 7390.44829 64.80067
Decay blank solution t2 546351.31687 2575.85955
Figure S11 Left: decay profile of PMO@Tb_phen sample in solid-state form, right: decay profile of PMO@Tb_phen sample in suspension. The decay times were recorded when exciting into the maximum of the broad ligand band and monitoring at the 5D4→7F5 transition peak.
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0 1 2 3 4
Inte
nsity
(a.u
.)
Time (ms)
Decay PMO@Eu_phen solid decay fit Model ExpDec2
Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr 2066.64911
Adj. R-Square 0.99982Value Standard Error
0.00000000E+0 y0 4.21621 4.20938
0.00000000E+0 A1 2913.73584 559.48329
0.00000000E+0 t1 475141.30178 31672.44398
0.00000000E+0 A2 28306.22225 509.79095
0.00000000E+0 t2 224168.91717 2434.25121
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Inte
nsity
(a.u
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Time (ms)
Decay PMO@Eu_phen suspension decay fit Model ExpDec2
Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr 373.07179
Adj. R-Square 0.99899Value Standard Error
0.00000000E+0 y0 7.01231 1.26754
0.00000000E+0 A1 933.48969 88.32954
0.00000000E+0 t1 654664.68787 25487.26558
0.00000000E+0 A2 3533.14817 82.15671
0.00000000E+0 t2 288376.17365 4096.76319
Figure S12 Left: decay profile of PMO@Eu_phen sample in solid-state form, right: decay profile of PMO@Eu_phen sample in suspension. The decay times were recorded when exciting into the maximum of the broad ligand band and monitoring at the 5D0→7F2 transition peak.
0 1 2 3 4
Inte
nsity
(a.u
.)
Time (ms)
PMO@Tb_bpy solid decay fit Model ExpDec2
Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr
803.17833
Adj. R-Square 0.99952Value Standard Error
decay solid y0 7.44892 1.00746decay solid A1 4174.32913 136.27713decay solid t1 215004.38375 4622.68653decay solid A2 5449.35676 152.77832decay solid t2 463118.99332 4467.18701
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Inte
nsity
(a.u
.)
Time (ms)
Decay PMO@Tb_bpy suspension decay fit Model ExpDec2
Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr 827.65139
Adj. R-Square 0.99929Value Standard Error
Decay blank solution y0 16.03301 1.56557
Decay blank solution A1 1325.92786 39.79316
Decay blank solution t1 233750.22604 8509.23896
Decay blank solution A2 4681.05739 49.57497
Decay blank solution t2 709831.5524 4274.83344
Figure S13 Left: decay profile of PMO@Tb_bpy sample in solid-state form, right: decay profile of PMO@Tb_bpy sample in suspension. The decay times were recorded when exciting into the maximum of the broad ligand band and monitoring at the 5D4→7F5 transition peak.
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0 1 2 3 4
Inte
nsity
(a.u
.)
Time (ms)
Decay PMO@Eu_bpy solid decay fit
Model ExpDec2Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr
272.81163
Adj. R-Square 0.99897Value Standard Error
Decay solid y0 0.43901 0.51567Decay solid A1 2429.73205 396.9925Decay solid t1 282017.39731 13140.3939Decay solid A2 1649.73161 405.37277Decay solid t2 442682.06498 22243.23705
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Inte
nsity
(a.u
.)
Time (ms)
Decay PMO@Eu_bpy suspension decay fit Model ExpDec2
Equation y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr 759.47112
Adj. R-Square 0.99971Value Standard Error
Decay blank solution
y0 9.40088 1.02916
Decay blank solution
A1 12604.21636 117.96361
Decay blank solution
t1 261617.3143 1604.75125
Decay blank solution
A2 2381.93182 131.39395
Decay blank solution
t2 571214.45642 11256.00743
Figure S14 Left: decay profile of PMO@Eu_bpy sample in solid-state form, right: decay profile of PMO@Eu_bpy sample in suspension. The decay times were recorded when exciting into the maximum of the broad ligand band and monitoring at the 5D0→7F2 transition peak.
Table S8 Luminescence decay times of studied materials
Sample τ1(µs) τ 2 (µs)
PMO@Tb solid 1004 350
PMO@Tb suspension 879 -
PMO@Eu solid 459 224
PMO@Eu suspension 1226 296
PMO@Tb_phen 359 62
PMO@Tb_suspension 546 159
PMO@Eu_phen solid 475 224
PMO@Eu_phen suspension
654 288
PMO@Tb_bpy solid 463 215
PMO@Tb_bpy suspension
710 234
PMO@Eu_bpy solid 443 282
PMO@Eu_bpy suspension
571 262
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0 2 4 6
Inte
nsity
(a.u
.)
Time (ms)
decay 0 M decay 17.9 M decay 89.5 M decay 179 M
Figure S15. Luminescence decay times of PMO@Tb_bpy observed at different concentrations. A reduction in the lifetime suggests a dynamic quenching mechanism.
0 50 100 150
0
500
100045C25C
I 0/I
Fe concentration (M)
Figure S16. The Stern-Volmer curves of PMO@Tb_bpy in the presence of Fe2+ ions at different temperatures (25 ºC and 45 ºC).
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Pb
Pb+Cr
Pb+Hg
Pb+Zn
Pb+Cu
Pb+Ca
Pb+Co
Pb+Fe
Pb+Mn
Wavelength (nm) 400 450 500 550 600 650
Cr
Cr+Pb
Cr+Hg
Cr+Zn
Cr+Cu
Cr+Ca
Cr+Co
Cr+Fe
Cr+Mn
Wavelength (nm)
Figure S17. Emission spectra of PMO@Tb_bpy in the presence of Pb2+ and competing ions (left) and Cr3+ and competing ions (right).
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
d
e
f
Figure S18 RT solid-state combined excitation-emission spectrum of PMO@Eu,Tb. The emission spectrum was recorded when exciting into the maximum of the broad ligand band and the excitation spectrum was monitored at the 5D4→7F5 transition peak.
Table S9 Assignment of peaks labeled in Figure S18 (PMO@Eu,Tb in solid-state).Label Wavelength (nm) Transitions
Excitationa 282 π→π*
Emissionb 488 5D4→7F6 (Tb)c 543 5D4→7F5 (Tb)d 589 5D0→7F1 (Eu)/ 5D4→7F4 (Tb)e 616 5D0→7F2 (Eu)f 699 5D0→7F4 (Eu)
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
d
e
f
Figure S19 RT solid-state combined excitation-emission spectrum of PMO@Eu,Tb_phen. The emission spectrum was recorded when exciting into the maximum of the broad ligand band and the excitation spectrum was monitored at the 5D0→7F2 transition peak.
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Table S10 Assignment of peaks labeled in Figure S19 (PMO@Eu,Tb_phen in solid-state).Label Wavelength (nm) Transitions
Excitationa 300 π→π*
Emissionb 488 5D4→7F6 (Tb)c 543 5D4→7F5 (Tb)d 588 5D0→7F1 (Eu)/ 5D4→7F4 (Tb)e 616 5D0→7F2 (Eu)f 698 5D0→7F4 (Eu)
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Inte
nsity
(a.u
.)
Wavelength (nm)
excitation emission
a
b
c
d
e
f
Figure S20 RT solid-state combined excitation-emission spectrum of PMO@Eu,Tb_bpy. The emission spectrum was recorded when exciting into the maximum of the broad ligand band and the excitation spectrum was monitored at the 5D4→7F5 transition peak.
Table S11 Assignment of peaks labeled in Figure S20 (PMO@Eu,Tb_bpy in solid-state).Label Wavelength (nm) Transitions
Excitationa 319 π→π*
Emissionb 488 5D4→7F6 (Tb)c 544 5D4→7F5 (Tb)d 589 5D0→7F1 (Eu)/ 5D4→7F4 (Tb)e 617 5D0→7F2 (Eu)f 700 5D0→7F4 (Eu)
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Figure S21 Photo taken under the UV lamp (302 nm excitation) of the PMO@Eu,Tb (left), PMO@Eu,Tb_phen (center) and PMO@Eu,Tb_bpy (left) samples.
solid water MeOH EtOH n-butanol iso-prop. DMF chloroform acetone
Inte
nsity
(a.u
.)
544 nm 614 nm
Figure S22 Bar graph representing the ratio of the 544 nm and 614 nm emission peaks in the PMO@Eu,Tb material dispersed in different solvents.
Figure S23 CIE color diagram showing the color change for PMO@Eu,Tb when dispersed in different solvents.
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solid water methanol ethanol n-butanol iso-prop. DMF chloroform acetone
Inte
nsity
(a.u
.)
543 nm 612 nm
Figure S24 Bar graph representing the ratio of the 543 nm and 612 nm emission peaks in the PMO@Eu,Tb_phen material dispersed in different solvents.
solid water MeOH EtOH n-butanol iso-prop. DMF chloroform acetone
Inte
nsity
(a.u
.)
542 nm 617 nm
Figure S25 Bar graph representing the ratio of the 542 nm and 617 nm emission peaks in the PMO@Eu,Tb_bpy material dispersed in different solvents.
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