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A series of europium-based metal organic frameworks with tuned intrinsic luminescence
properties and detection capacities
Pengda Yi, Hongliang Huang*, Yaguang Peng, Dahuan Liu* and Chongli Zhong
State Key Laboratory of Organic-Inorganic Composites, Beijing University of
Chemical Technology, Beijing 100029, China
Corresponding Author: Hongliang Huang, E-mail: [email protected];
Dahuan Liu, E-mail: [email protected]
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
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TABLE OF CONTENTS
1. Crystal data and structure refinement ...............................................3
2. SEM images FT-IR spectra and TGA curves ....................................4
3. Luminescence lifetime and fluorescence quantum yield...................6
4. Sensing of anions ..................................................................................7
5. Sensing of organic solvent molecules ..................................................9
6. Sensing of metal ions ..........................................................................11
7. Photographs in various analytes under UV-light irradiation ........13
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1. Crystal data and structure refinement
Table S1 Crystal data and structure refinement for Eu-BDC-NH2
Eu-BDC-NH2 (CCDC: 1494828)Empirical formula C104H132Eu12N16O76
Formula weight 4644.703Measurement temperature 282(1) K
Crystal system CubicSpace group Fm-3m
a (Å) 21.713(3)b (Å) 21.713(3)c (Å) 21.713(3)α (°) 90β (°) 90γ (°) 90
Volume(Å3) 10237(2)Z 2
Calculated density(g/cm3) 1.610Absorption coefficient (mm-1) 26.572
Independent reflections (I > 2σ(I)) 515 [R(int) = 0.0345]F(000) 4744
Reflections collected 3527Completeness to theta = 66.98 o 100.0 %
θ range for data collection 3.53-66.98Data/restraints/parameters 515/14/32
Limiting indices –25 ≤ h ≤ 12–21 ≤ k ≤ 25–18 ≤ l ≤ 17
Goodness-of-fit on F2 1.147R1
a,wR2b [I > 2σ(I)] R1 = 0.0900, wR2 = 0.2544R1
a, wR2b (all data) R1 = 0.0930, wR2 = 0.2600
Largest diff. peak and hole (e/Å3) 1.697 and –3.912a R1 = (F0FC)/F0. b wR2 = [w(F02FC2)2/w(F0
2)]1/2.
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2. SEM images FT-IR spectra and TGA curves
Fig. S1 SEM images for Eu-MOFs
500 1000 1500 2000 2500 3000 3500 4000
1000-1150 cm-1
1660 cm-1
Tran
smitt
ance
Wavenumber/cm-1
Eu-1,4-NDC Eu-BDC-F Eu-BDC-NO2
Eu-BDC-NH2
1535 cm-1
Fig. S2 FT-IR spectra for Eu-MOFs
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100 200 300 400 500 600 70030
40
50
60
70
80
90
100
Wei
ght (
%)
Temperature (.C)
Eu-BDC-NH2
100 200 300 400 500 600 70030
40
50
60
70
80
90
100
Wei
ght (
%)
Temperatuer (.C)
Eu-BDC-NO2
100 200 300 400 500 600 700
40
50
60
70
80
90
100
Wei
ght (
%)
Temperature (.C)
Eu-1,4-NDC
100 200 300 400 500 600 70030
40
50
60
70
80
90
100
Weig
ht (%
)
Temperature (.C)
Eu-BDC-F
Fig. S3 TGA curves for Eu-MOFs
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3. Luminescence lifetime and fluorescence quantum yield
0 2 4 6 8 10
Inte
nsit
y / a
.u.
Decay time / ms
Eu-1,4-NDC Eu-BDC-F Eu-BDC-NH2
Fig. S4 Luminescence lifetime for Eu-MOFs
Table S2 The quenching efficiencies of the Eu-MOFs in various analytes
Ligands BDC-NH2 BDC-F 1,4-NDC
Fluorescence quantum yield 1.24% 3.40% 35.77%
Lifetime (ns) 4.88 2.17 21.1
MOFs Eu-BDC-NH2 Eu-BDC-F Eu-1,4-NDC
Fluorescence quantum yield 3.21% 30.83% 57.01%
Lifetime (ms) 0.54 0.72 1.06
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4. Sensing of anions
550 600 650 700
Rel
ativ
e In
tens
ity
/ a.u
.
Wavelength / nm
Cr 2
O72-
0 10μM 20μM 30μM 60μM 80μM 200μM 360μM 500μM
Eu-1,4-NDC
550 600 650 700
Cr 2
O72-
0 10μM 20μM 30μM 60μM 80μM 200μM 360μM 500μM
Rel
ativ
e In
tens
ity /
a.u.
Wavelength / nm
Eu-BDC-F
550 600 650 700
Wavelength / nm
Cr 2
O72-
0 10μM 20μM 30μM 60μM 80μM 200μM 360μM 500μM
Rel
ativ
e In
tens
ity /
a.u.
Eu-BDC-NH2
.
Rel
ativ
e In
tens
ity /
a.u.
Eu-1,4-NDC
I-Br-
NO 3-
Ac-
HCO 3-
SO4
2-
DMF
Cr 2O 7
2-
F-
CO 32-
NO 2-
Cl-
Rel
ativ
e In
tens
ity /
a.u.
Eu-BDC-F
I-Br
-
NO 3-
Ac-
HCO 3-
SO4
2-
DMF
Cr 2O 7
2-
F-
CO 32-
NO 2-
Cl-
Rel
ativ
e In
tens
ity /
a.u.
Eu-BDC-NH2
I-Br-
NO 3-
Ac-
HCO 3-
SO4
2-
DMF
Cr 2O 7
2-
F-
CO 32-
NO 2-
Cl-
Fig. S5 The PL intensities of Eu-MOFs toward with various anions and in various concentrations of Cr2O7
2- solution.
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200 250 300 350 400
0
1
2
AB
s
Wavelength / nm
Cl-
Cr2O72-
F-
HCO3-
SO42-
NO2-
CO32-
I-
NO3-
Br-
Ac-
298nm280nm278nm
Fig. S6 Liqiud UV−vis absorption spectra of different anions.
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5. Sensing of organic solvent molecules
550 600 650 700
0 0.1% 0.2% 0.3% 0.4% 0.5% 0.8% 1.0% 2.0%
acet
one
Rel
ativ
e In
tens
ity /
a.u.
Wavelength / nm
Eu-1,4-NDC
550 600 650 700
Rel
ativ
e In
tens
ity /
a.u.
Wavelength / nm
0 0.1% 0.2% 0.3% 0.4% 0.5% 0.8% 1.0% 2.0%
acet
one
Eu-BDC-F
550 600 650 700
acet
one
0 0.1% 0.2% 0.3% 0.4% 0.5% 0.8% 1.0% 2.0%
Rel
ativ
e In
tens
ity /
a.u.
Wavelength / nm
Eu-BDC-NH2
.
CH 3CN
NMP
DMA THF
Rel
ativ
e In
tens
ity /
a.u.
Eu-1,4-NDC
Ethyl
aceta
te
CH 2Cl 2
DMF
Aceton
e
Ether
CHCl 3
C 2H5OH
CH 3OH
CH 3CN
NMP
DMA THF
Rel
ativ
e In
tens
ity /
a.u.
Eu-BDC-F
Ethyl a
cetat
e
CH 2Cl 2
DMF
Aceton
e
Ether
CHCl 3
C 2H5OH
CH 3OH
CH 3CN
NMP
DMA THF
Rel
ativ
e In
tens
ity /
a.u.
Eu-BDC-NH2
Ethyl a
cetat
e
CH 2Cl 2
DMF
Aceton
e
Ether
CHCl 3
C 2H5OH
CH 3OH
Fig. S7 The PL intensities of Eu-MOFs with various pure organic solvents and in various concentrations of acetone solution.
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200 220 240 260 280 300 320 340 360
0.0
0.5
1.0
1.5
2.0
2.5
3.0
AB
s
Wavelength / nm
acetone CH2Cl2
MeOH CH3Cl3
EtOH Ether Ethyl acetate CH3CN DMA NMP THF
298nm280nm278nm
Fig. S8 Liqiud UV−vis absorption spectra of different solvents.
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6. Sensing of metal ions
550 600 650 700
Rel
ativ
e In
tens
ity /
a.u.
Wavelength / nm
0 10μM 20μM 30μM 60μM 80μM 200μM 360μM 500μM
Fe3+
Eu-1,4-NDC
550 600 650 700
Fe3+
0 10μM 20μM 30μM 60μM 80μM 200μM 360μM 500μM
Rel
ativ
e In
tens
ity /
a.u.
Wavelength / nm
Eu-BDC-F
550 600 650 700
Fe3+
0 10μM 20μM 30μM 60μM 80μM 200μM 360μM 500μM
Rel
ativ
e In
tens
ity /
a.u.
Wavelength / nm
Eu-BDC-NH2
Eu-1,4-NDC
Rel
ativ
e In
tens
ity /
a.u.
Na+
Zn2+
Al3+
Pb2+
Ag+
K+
Hg2+
DMF Fe3+
Mg2+
Mn2+
Ni2+
Eu-BDC-F
Rel
ativ
e In
tens
ity /
a.u.
Na+
Zn2+
Al3+
Pb2+
Ag+ K
+Hg
2+
DMFFe
3+
Mg2+
Mn2+
Ni2+
Eu-BDC-NH2
Rel
ativ
e In
tens
ity /
a.u.
Na+
Zn2+
Al3+
Pb2+
Ag+ K
+Hg
2+
DMFFe3
+
Mg2+
Mn2+
Ni2+
Fig. S9 The PL intensities of Eu-MOFs toward various ions and in various concentrations of Fe3+ solution.
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10 20 30 40 50
R
elat
ive
Inte
nsi
ty /
a.u
.
2 Theta / degree
Eu-1,4-NDC Fe3+@Eu-1,4-NDC
10 20 30 40 50
Rel
ativ
e In
ten
sity
/ a.
u.
2 Theta / degree
Eu-BDC-F Fe3+@Eu-BDC-F
10 20 30 40 50
Rel
ativ
e In
ten
sity
/ a.
u.
2 Theta / degree
Eu-BDC-NH2
Fe3+@Eu-BDC-NH2
Fig. S10 PXRD patterns of the original and ions exchanged compounds.
Table S3 The detailed ICP studies of Eu-MOFs and target metal ions
Sample Eu3+(ppm) Fe3+(ppm)Eu-BDC-NH2 19.10 1.496
Eu-BDC-F 12.44 2.478Eu-1,4-NDC 20.04 2.083
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7. Photographs in various analytes under UV-light irradiation
Eu-1
,4-N
DC
Eu-B
DC
-FEu
-BD
C-N
H2
DMF Fe3+ Cr2O72- acetone
Fig. S11 The photographs of Eu-MOFs in the analytes solutions (10-2M) under UV-light