Electronic Supplementary Information

Secondary-amine-functionalized isoreticular

metal–organic frameworks for controllable and selective

dye capture

Jing Tan,# Beibei Zhou,# Congcong Liang, Hannah Zinky, Hao-Long Zhou and

Yue-Biao Zhang*

School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210,

China.

Email: zhangyb@shanghaitech.edu.cn

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.This journal is © the Partner Organisations 2017

Table S1. Crystal data and structure refinements results.

Compound ST-14 ST-15

Formula C42H28N10O8Cu2 C42H28N10O8Zn2

Formula weight 927.82 931.48

Crystal system cubic cubic

Space group P-43n (No.218) P-43n (No.218)

a (Å) 27.6887(13) 28.1049(10)

V (Å3) 21228(3) 22200(2)

Z 6 6

Crystal size (mm3) 0.12 × 0.12 × 0.12 0.12 × 0.12 × 0.12

T (K) 173 173

(Å) 1.54178 1.54178

range (°) 2.26–42.9 3.14–43.0

Total reflections 68406 32606

Unique reflections 2572 2690

Rint 0.0636 0.0439

Observed Data 2572 2690

Resolution (Å) 1.10 1.10

R1, wR2 (I > 2σ) 0.0200, 0.0517 0.0322, 0.0810

R1, wR2 (all) 0.0225, 0.0535 0.0363, 0.0826

S 1.156 1.104 a R1=∑||Fo|−|Fc||/∑|Fo|.

b wR2={∑w[(Fo)2−(Fc)2]2/∑w[(Fo)2]2}1/2

Table S2. Crystal data and structure refinements results.

Structure

3D structure

Name Methylene Blue Rhodamine B Crystal Violet Solvent Yellow

2 Acid Red 88 Orange G New Coccine

Abbr MLB RHB CV SY2 AR88 OG NC

Charge +1 +1 +1 0 -1 -2 -3

MW. 373.90 479.01 407.98 225.30 400.383 452.37 604.47

Optimal

absorption

wavelength

655 547 589 405 510 499 514

Inclusion Y Y Y N N N N

Dimension

(10-10m)

x = 4.00

y = 7.93

z =16.34

x = 6.53

y = 11.89

z = 15.55

x = 4.77

y = 12.43

z = 13.09

x = 4.5

y = 6.0

z = 15.1

x = 5.44

y = 10.27

z = 15.66

x = 5.44

y = 10.14

z = 15.64

x =5.44

y =10.48

z =17.38

4000 3600 3200 2800 2400 2000 1600 1200 800 400

ST-14

Wavelength (nm)

ST-15

 

Fig. S1 IR spectra of ST-14 and ST-15. 

Fig. S2 Asymmetric unit in the single crystal structure of (a) ST-14 and (b) ST-15 (thermal

ellipsoids with 50% probability; Carbon, grey; Nitrogen, blue; Oxygen, red; Zinc, light-blue;

Copper, yellow.). Hydrogen atoms are omitted for clarity; symmetry-related atoms are not

labelled and represented as spheres.   

0 100 200 300 400 500 600 700

20

40

60

80

100ST-14

(a)

Wei

ght

loss

(%

)

Temperature (oC)  

0 100 200 300 400 500 600 700

20

40

60

80

100

Temperature (oC)

Wei

ght

loss

(%

)

ST-15(b)

 

Fig. S3 TG curves of (a) ST-14 and (b) ST-15.

 

Fig. S4. 1H NMR spectrum of ST-15 digested in DMSO-d6 with DCl. Integration of the

chemical shifts provides the linker molar ratio of TATAB and BPY round to 4:3, which is

consistent with that of the crystallographic analysis result.

Fig. S5 Photographs of the monocomponent dye solution with the presence of (a) ST-14 and

ST-15, compared with (b) other TATAB-based MOFs (meso-PCN and PCN-100).

400 500 600 700

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

MLB

400 450 500 550 600 650

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

RHB

 

350 450 550 650Wavelength (nm)

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

CV

350 400 450 500 550 600

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

SY2

 

350 450 550 650

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

AR88

350 400 450 500 550 600

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

OG

 

350 450 550 650

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

NC

Fig. S6 UV-vis spectra changes of monocomponent dye solution with the presence of ST-15.

4 8 12 16 20 24

(a)ST-14-CV

ST-14-RHB

ST-14-MLB

ST-14 as-synthesized

Inte

nsity

2 (o)4 8 12 16 20 24

ST-14 as-synthesized

ST-14-SY2

ST-14-AR88

ST-14-OG

ST-14-NC

2 (o)

Inte

nsity

4 8 12 16 20 24

2 (o)

ST-15 as-synthesized

ST-15-MLB

ST-15-RHB

ST-15-CV

Inte

nsity

(b)

4 8 12 16 20 24

ST-15 as-synthesized

ST-15-SY2

ST-15-AR88

ST-15-OG

ST-15-NC

2 (o)

Inte

nsity

 

Fig.S7 Powder X-ray diffraction patterns of (a) ST-14 and (b) ST-15 after dye adsorption

experiments.

400 500 600 700

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

MLB

400 450 500 550 600 650

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

RHB

 

350 450 550 650

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

CV

350 400 450 500 550 600

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

SY2

350 450 550 650

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

AR88

350 400 450 500 550 600

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

OG

350 450 550 650

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

NC

 

Fig. S8 UV-vis spectra changes of monocomponent dye solution with the presence of ST-14.

0 100 200 300 400 500

0

20

40

60

80

100

CV (Z=+1)

RHB (Z=+1)

NC (Z = -3)OG (Z = -2)AR88 (Z = -1)SY2 (Z=0)

MLB (Z=+1)

Dye

ret

entio

n in

sol

utio

n (%

)

Time (min)  

Fig. S9 Differently charged dyes contents in solution with presence of ST-14 monitored with

time.

350 450 550 650 750

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)

(a)

 350 450 550 650 750

(b)

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)  

350 450 550 650 750

(c)

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)  350 450 550 650 750

(d)

0 min 30 min 60 min 120 min 180 min 240 min 300 min 360 min 420 min 480 min

Wavelength (nm)  

Fig. S10 UV-vis spectra changes of mixed dye solution with the presence of ST-14. The

photographs show the colours of the dye solutions, their mixture before and after adsorption.

0 200 400 600 800 1000 1200 1400 1600 1800

0

20

40

60

80

100 ST-14 ST-15

Time (min)

Dye

re

ten

tion

in s

olu

tion

(%

)

Fig. S11 MLB contents in solution with presence of ST-14 and ST-15 monitored with by 30

hours, confirming that the samples of ST-14 and ST-15 possessed similar adsorption capacity

but different adsorption kinetics.

4 8 12 16 20 24

ST-15-MLB-desorption

ST-15-MLB

ST-15 as-synthesized

Inte

nsity

2()  

Fig.S12 Powder X-ray diffraction patterns of ST-15 after dye release experiments.