1
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
2
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
3
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.
4
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
5
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
6
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
7
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.
8
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.
9
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.
10
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.
11
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.
12
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
13
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
