Organosilica Hybrid MaterialsTable 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

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).

S1

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2019

250 300 350 400 450 500 550 600

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).

250 300 350 400 450 500 550 600 650

Inte

nsity

(a.u

.)

Wavelength (nm)

excitation emission

a

b

c

d e

250 300 350 400 450 500 550 600 650

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

S2

250 300 350 400 450 500 550 600 650 700 750

Inte

nsity

(a.u

.)

Wavelength (nm)

excitation emission

a

b cd e

f

g

h

i

250 300 350 400 450 500 550 600 650 700 750

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

S3

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


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


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


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.

250 300 350 400 450 500 550 600 650

Inte

nsity

(a.u

.)

Wavelength (nm)

excitation emission

a

b

c

de

250 300 350 400 450 500 550 600 650

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



c 543 5D4→7F5

d 583 5D4→7F4

S4

e 620 5D4→7F3

250 300 350 400 450 500 550 600 650 700 750

Inte

nsity

(a.u

.)

Wavelength (nm)

excitation emission

a

b

c

d

e

f

250 300 350 400 450 500 550 600 650 700 750

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

S5

250 300 350 400 450 500 550 600 650

Inte

nsity

(a.u

.)

Wavelength (nm)

excitation emission

a

b

c

d e

250 300 350 400 450 500 550 600 650

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



c 543 5D4→7F5

d 583 5D4→7F4

e 620 5D4→7F3

250 300 350 400 450 500 550 600 650 700 750

Inte

nsity

(a.u

.)

Wavelength (nm)

excitation emisison

a

b

c d

e

f

g

h

250 300 350 400 450 500 550 600 650 700 750

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.

S6

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


Reduced Chi-Sqr

19759.30571


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




Decay blank solution y0 24.21144 1.34546

Decay blank solution A1 10594.36328 48.32454

Decay blank solution t1 158785.77361 1464.13453



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.

S7

0 1 2 3 4

Inte

nsity

(a.u

.)

Time (ms)

Decay PMO@Eu_phen solid decay fit Model ExpDec2




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

0 1 2 3 4

Inte

nsity

(a.u

.)

Time (ms)

Decay PMO@Eu_phen suspension decay fit Model ExpDec2




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


Reduced Chi-Sqr

803.17833


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

0 1 2 3 4

Inte

nsity

(a.u

.)

Time (ms)

Decay PMO@Tb_bpy suspension decay fit Model ExpDec2




Decay blank solution y0 16.03301 1.56557





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.

S8

0 1 2 3 4

Inte

nsity

(a.u

.)

Time (ms)

Decay PMO@Eu_bpy solid decay fit


Reduced Chi-Sqr

272.81163


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

0 1 2 3 4

Inte

nsity

(a.u

.)

Time (ms)

Decay PMO@Eu_bpy suspension decay fit Model ExpDec2




Decay blank solution

y0 9.40088 1.02916


A1 12604.21636 117.96361


t1 261617.3143 1604.75125


A2 2381.93182 131.39395


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

S9

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).

400 450 500 550 600 650

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).

S10

250 300 350 400 450 500 550 600 650 700 750

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


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)

250 300 350 400 450 500 550 600 650 700 750

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.

S11

Table S10 Assignment of peaks labeled in Figure S19 (PMO@Eu,Tb_phen in solid-state).Label Wavelength (nm) Transitions



250 300 350 400 450 500 550 600 650 700 750

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



S12

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.

S13

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.

S14

Documents

Organosilica Hybrid MaterialsTable 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