Supplementary Information

For

A nitrogen-rich fluorescent conjugated microporous polymer

with triazine and triphenylamine units for high iodine capture

and nitro aromatic compounds detection

Tongmou Geng*a, Zongming Zhua, Weiyong Zhanga, and Yu Wangb

a. Anhui Provincial Laboratory of Optoelectronic and Magnetism Functional Materials;

Anhui Key Laboratory of Functional Coordination Compounds; School of Chemistry and

Chemical Engineering, Anqing Normal University, Anqing 246011, P. R. China

b School of Resource and Environmental Science, Anqing Normal University, Anqing 246133,

P. R. China

Corresponding Author:

Tongmou Geng

Mailing Address: School of Chemistry and Chemical Engineering, Anqing Normal University,

Anqing 246011, China

Telephone: +86-0556-5500090

Fax: +86-0556-5500090

E-mail addresses: gengtongmou@aqnu.edu.cn (TM Geng).

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2017

Table of contents

I. The SEM images of TTPB with different reaction time………………………… S3

II. Photographs of dispersion of the TTPB in different solvents with UV light

irradiation (365 nm) ………………………………………………………………..S4

III. PXRD datum………………………………………………………..…………. S5

IV. Thermal stability of TTPB…………………………………..……………….… S6

V. The FTIR spectrum of the TTPB……………………………….…………….….S7

VI. ss 13C NMR spectrum of TTPB……………………………………….…….….S8

VII. The absorption spectra of TTPB and TPB…………………………………..…S9

VII. Pore and surface properties of TTPB………………………………….………S10

VIII. Summary of surface area and iodine sorption properties of TTPB……. .…S11

Ⅸ. Release and adsorption properties of iodine……………………………………S13

Ⅹ. Fluorescence spectra of TTPB………………………………………………… S15

I. The SEM images of TTPB with different reaction time

Fig. S1 The SEM images of TTPB with different reaction time (a) 12 h and (b) 24 h.

II. Photographs of dispersion of the TTPB in different solvents with

UV light irradiation at 365 nm

Fig. S2 Photographs of dispersion of the TTPB in different solvents with UV light

irradiation at365 nm. The reaction time: (a) 12 h and (b) 24 h.

III. PXRD datum

0 10 20 30 40 50 60 2Theta/degree

Fig. S3 PXRD pattern of TTPB.

IV. Thermal stability of TTPB

0 100 200 300 400 500 600 700 800

60

70

80

90

100

Temperature (oC)

Weig

ht L

oss (

%)

Fig. S4 Thermogravimetric analysis (TGA) image of TTPB.

V. The FTIR spectrum of the TTPB

4000 3500 3000 2500 2000 1500 1000 50075

80

85

90

95

100

Tran

smitt

ance

/ %

Wavenumber/cm-1

3033.213435.84

697.76735.63805.961274.281383.25

1492.211601.18

TTPB

Fig. S5 The FTIR spectrum of the TTPB

VI. ss 13C NMR spectrum of TTPB

Fig. S6 ss 13C NMR spectrum of TTPB.

VII. The absorption spectra of TTPB and TPB

300 350 400 450 500 550 600

0

1

2

3

4

350.24

277.34

371.28

277.87

Abs

Wavelength (nm)

TPB TTPB

Fig. S6 The absorption spectra of TTPB (red line) dispersed in DOX and its monomer

(TPB) in DOX (black line).

VII. Pore and surface properties of TTPB

Table S1 Pore and surface properties of TTPB.

CMPs SBETa

(m2 g-1)

SLangmuira

(m2 g-1)

Vtotal

(tpv)b

(cm3 g-1)

Vmicroc

(cm3 g-1)

Vmicro/

Vtotal

Smicroc

(m2 g-1)

Sexternalc

(m2 g-1)

TTPB 222.25 301.41 0.1271 0.05783 45.18 126.51 95.74

a Specific surface area calculated from the adsorption branch of the nitrogen isotherm

using the BET method in the relative pressure (P/P0) range from 0.01 to 0.10.

b Total pore volume is obtained from BET data up to P/P0=0.97 and is defined as the

sum of micropore volume and volume of larger pores.

c Micropore volume calculated from nitrogen adsorption isotherm using the t-plot

method.

VIII. Summary of surface area and iodine sorption properties of

CMPs

Table S 2 Summary of surface area and iodine sorption properties of CMPs.

Sample

(heteroatom)

BET

(m2 g-1)

T (oC) Iodine uptake

(g g-1)

Ref

NiP-CMPs

(N)

2600 77 202 [6]Chem. Commun. 2014, 50,

8495-8498.

PAF-1(no N, S),

JUC-Z2 ( N )

5600,

2081

25 1.86, 1.44 [5]J. Mater. Chem. A, 2014, 2,

7179–7187.

CMPN-1,CMPN-2,

CMPN-3 (no N, S)

1368 70.3 0.97, 1.10,

2.08

[11]J. Mater. Chem. A, 2015, 3,

87–91.

PAF-23, PAF-24,

PAF-25 (B, Li+)

82, 136,

262

75 2.71, 2.76,

2.60

[4]Angew. Chem. Int. Ed., 2015,

54, 12733 –12737.

Azo-Trip

(N)

510.4 77 2.33 [3]Polym. Chem., 2016, 7, 643–

647.

SCMP-1, SCMP-2

(S)

413, 855 80 1.88, 2.22 [2]ACS Appl. Mater. Interfaces,

2016, 8, 21063−21069.

SCMP-I, SCMP-II

(S)

2.72,

119.76

80 3.45 [1]Chem. Commun., 2016, 52,

9797-9800.

Por-Py-CMP

(N)

1014 77 1.30 RSC Adv., 2016, 6, 75478–

75481.

HCMP-1, -2, -3, -4

(N)

430, 153,

82, n.a.

85 1.59, 2.81,

3.16, 2.22

[7]Macromolecules, 2016, 49,

6322−6333.

NTP

(N)

COP10

(N, P, O)

BQCMP-1,

DQCMP-1(N)

CMP-3

(N)

PAF- 21,-22

(B)

N APOP-1,-2,

-3,-4 (N)

1067

-

422,

123

739.8

104, -

1000,658,

1008, 926

75

60

80

r.t

75

75

1.80

3.80

1.51,

1.61

0.218

(in solution)

1.52, 1.96

2.06, 2.39,

2.41, 2.65

[24]ACS Macro Lett., 2016, 5,

1039−1043.

[25]J. Mater. Chem. A, 2016,

4(4): 15361-15369.

Macromol. Mater. Eng.

2016, 301, 1104−1110.

React. Funct. Polym. 106

(2016) 105–111.

Acta Chim. Sinica

2016, 74, 67−73.

[17]J. Polym. Sci., Part A:

Polym. Chem. 2016, 54, 1724–

1730.

TTPB (N) 222 77 4.43 This work.

Ⅸ. Release and adsorption properties of iodine

0 100 200 300 400 500 600 700 800

20

40

60

80

100

Temperature (oC)

Weig

ht L

oss (

%)

I2@TPPB(2)

Fig. S7 TGA trace of I2@TTPB.

200 300 400 500 600 700 800

0.0

0.5

1.0

1.5

2.0

2.5

(a)

Abs

Wavelength (nm)

10mg L-1

20mg L-1

40mg L-1

5mg L-1

0 10 20 30 40

0.0

0.5

1.0

1.5

2.0

I2/EthanolR=0.9943

Concentration (mg L-1)

Abs

(b)

Fig. S8 (a) Calibration plot of standard iodine by UV/vis spectra in ethanol solution;

(b) The fitting of Abs value vs concentration of I2 with the relatively good linearity

satisfies Lambert-Beer Law.

40

50

60

70

80

90

100

40

50

60

70

80

90

100

54321Recycling percentage

Recy

cling

per

cent

age (

%)

Iodi

ne u

ptak

ing

perc

entag

e (%

)

Iodine uptaking percentage (%) Recycling percentage (%)

Fig. S9 Recycling percentage of TTPB (recycling parameters: 350 K, 22 h and 398 K,

60 min).

Ⅹ. Fluorescence spectra of TTPB

300 400 500 600 700 8000

50

100

150

200

250

300

350

Wavelength (nm)

Fluo

resc

ence

Inten

sity

(a.u

.)

Acetone DMF DOX Chloroform Ethanol THF

Fig. S10 Fluorescence emission spectra of the TTPB in ACN, acetone, DMF, DOX,

chloroform, THF and ethanol, respectively (0.5 mg mL-1), excited with the same

wavelength at 370 nm.

300 400 500 600 700 8000

50

100

150

200

250

300

350

(a)

Wavelength (nm)

Fluo

resc

ence

Inten

sity

(a.u

.)

NP

0 50 100 150 200 250 300

0

50

100

150

200

250

300

350

NP

(b)

Time (s)

Fluo

resc

ence

Inten

sity

(a.u

.)

300 400 500 600 700 800

0

50

100

150

200

250

300

350(c)

Wavelength (nm)

Fluo

resc

ence

Inten

sity

(a.u

.)

PA-time

0 50 100 150 200 250

150

200

250

300

350

Time (s)

Fluo

resc

ence

Inten

sity

(a.u

.)

PA

(d)

Fig. S11 (a,c) Normalized fluorescence intensity of the TTPB suspensed in DOX (0.5

mg mL-1) upon addition of NP and PA (5.0×103 mol L-1) for different periods of time.

(b,d) Degree of fluorescence quenching of the TTPB suspensed in DOX upon

different periods of time.

300 400 500 600 700 8000

50

100

150

200

250

300

350(a)

Fl

uore

scen

ce In

tensit

y (a

.u.)

Wavelength (nm)

300 400 500 600 700 8000

50

100

150

200

250

300

350

Wavelength (nm)

Fluo

resc

ence

Inten

sity

(a.u

.)

(b)

300 400 500 600 700 8000

50

100

150

200

250

300

350

(c)

Fluo

resc

ence

inten

sity

(a.u

)

Wavelength (nm)

300 400 500 600 700 8000

50

100

150

200

250

300

350

Wavelength (nm)

Fluo

resc

ence

Inten

sity

(a.u

.)

(d)

300 400 500 600 700 8000

50

100

150

200

250

300

350

Wavelength (nm)

Fluo

resc

ence

Inten

sity

(a.u

.)

(e)

300 400 500 600 700 8000

50

100

150

200

250

300

350

Wavelength (nm)

Fluo

resc

ence

Inten

sity

(a.u

.)

(f)

Fig. S12 Fluorescence spectral changes of TTPB suspension of DOX (0.5 mg mL-1)

upon addition of (a) DNT, (b) NP, (c) PA, (d) PhOH, (e) NB, and (f) NT (λex=370

nm).

Table S3 The equation of I0/I of TTPB to the concentrations of DNT, PA, NP, PhOH,

NT and NB for suspension in DOX.

The equation Regression

coefficient

(R)

The concentration range of

PA

(mol L-1)

detection limit

(mol L-1)

I0/I=1.082+1.94×102[DNT] 0.9993 1.5×10-4 to 5.0×10-4 -

I0/I=0.974+4.85×104[NP] 0.9987 0 to 2.0×10-4 4.64×10-10

I0/I=1.147+1.29×103[PA] 0.9981 1.5×10-5 to 5.0×10-3 8.14×10-9

I0/I=0.991-7.86×102[PhOH] -0.9211 0 to 5.0×10-5 -

I0/I=1.052+2.35×102[NT] 0.9974 2.5×10-5 to 5.0×10-3 -

I0/I=0.791+1.16×102[NB] 0.9980 5.0×10-5 to 6.0×10-3 -