properties and detection capacities - rsc. · PDF file1 A series of europium-based metal...

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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: huanghl@mail.buct.edu.cn;

Dahuan Liu, E-mail: liudh@mail.buct.edu.cn

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.

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.

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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