Triazine-based Conjugated Microporous Polymers with. N,N,N,N -Tetraphenyl-1,4-phenylenediamine, 1, 3, 5-

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1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 218 Triazine-based Conjugated Microporous Polymers with N,N,N,N -Tetraphenyl-1,4-phenylenediamine, 1, 3, 5- Tris(diphenylamino)benzene and 1,3,5-Tris[(3-methylphenyl)- phenylamino]benzene as the Core for High Iodine Capture and Fluorescence Sensing o-nitrophenol Tongmou Geng*, Sainan Ye, Zongming Zhu and Weiyong Zhang Collaborative Innovation Center for Petrochemical New Materials, AnHui Province Key Laboratory of Optoelectronic and Magnetism Functional Material, Anqing Normal University, Anqing 24611, China Corresponding Author: Tongmou Geng Mailing Address: School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 24611, China Telephone: Fax: addresses: (TM Geng).

2 EXPERIMENTAL SECTION Chemicals and reagents N,N,N,N -tetraphenyl-1,4-phenylenediamine (TPPA) 1,2-dichlorobenzene, 2,4,6-trichloro-1,3,5-triazine (TCT), methane-sulfonic acid, and 1,3,5-Tris[(3- methylphenyl)phenylamino]benzene (m-mtdab) were purchased from Aladdin reagent (Shanghai) Co. Ltd. and used as received. 1,3,5-Tris(diphenylamino)benzene (TDAB) was purchased from Shanghai Zhen Zhun biological science and technology Co. Ltd. and used as received. Unless otherwise noted, all other reagents and solvents were of analytical grade and used as supplied without further purification. Adsorbent Recycle Recycling percentage (Rp) of the adsorbents was determined as follows: 3 mg of iodine-equilibrium powders were charged in an open glass vial (1 ml) and heated at 398 K for 12 min in air dry oven. The recovered TCMPs powders were reused for iodine uptake at 35 K for 22 h. The recycling percentage were calculated by weight gains: Rp=Cu/Cu wt %, where Rp is the recycling percentage, Cu and Cu are the iodine uptake capacity of TCMPs before and after heating recovered. The same powders were recycled three times. The above-mentioned iodine uptake, release, and recycling percentage of adsorbents were average values that obtained from three measurements each. ( Macromolecules 216, 49, )

3 Measurements The infrared spectra were recorded from 4 to 4 cm -1 on an is5ft-ir spectrometer by using KBr pellets. Solid-state 13 C CP/MAS NMR measurements were recorded on a Bruker AVANCE III 4 WB spectrometer at a MAS rate of 5 khz and a CPcontact time of 2 ms. Elemental analyses were carried out on a VARIO ELIII cube analyzer. UV Vis spectra were recorded on an UV-251PC spectrometer. Scanning electron microscopy was performed on a S-34N microscope. X-ray diffraction data were recorded on a XRD6 diffractometer by depositing powder on glass substrate, from 2θ =5 up to 9 with.2 increment. Thermogravimetric analysis (TGA) measurements were performed on a CDR-4P TGA under N 2, by heating to 8 C at a rate of 1 C min 1. The Brunauer-Emmett-Teller (BET) method was utilized to calculate the specific surface areas and pore volume, the Saito- Foley (SF) method was applied for the estimation of pore size distribution. Raman spectra were acquired using a DXR equipped with a 532 nm diode laser. Fluorescence spectra were recorded on a RF-531PC spectrophotometer (Shimadzu). The samples were prepared as follows: dried CMPs powder (1 mg) ground with an agate mortar was added to 1 ml of organic solvents. After the resulting mixture was well dispersed with ultrasound, the dispersion colloid was obtained.

4 TTPPA (a) Wavenumber (cm -1 ) TTDAB (b) Wavenumber (cm -1 ) Tm-MTDAB (c) I2@Tm-MTDAB Wavenumber (cm -1 )

5 1 (d) Transmittance (%) Wavenumber (cm -1 ) Fig. S1. FT-IR spectra of CMPs, iodine-loaded CMPs and pristine iodine. (a) (b) (c) and (d). Table S1. Elemental analysis data of TTPPA, TTDAB and Tm-MTDAB wt% C H N TTPPA Anal. calcd Found TTDAB Anal. calcd Found Tm-MTDAB Anal. calcd Found

6 Abs (a) TCT TPPA TTPPA (b) TCT TDAB TTDAB Abs Abs (c) 256 TCT Tm-MTDAB m-mtdab Fig. S2. UV-Vis spectra of the solid-states of TCT, monomers and TCMPs. (a) TTPPA, (b) TTDAB and (c) Tm-MTDAB. 43

7 TTPPA TTDAB Tm-MTDAB Theta/degree Fig. S3. XRD patterns of TTPPA, TTDAB and Tm-MTDAB. Fig. S4. The representative SEM micrographs of TTPPA, TTDAB, and Tm-MTDAB. Scale: top: 1 μm, bottom: 3 μm.

8 Weight Loss (%) Weight Loss (%) Weight Loss (%) (a) (b) Temperature ( o C) (c) Temperature ( o C) Temperature ( o C) Fig. S5. Thermogravimetric analysis (TGA) curvers of (a) TTPPA (b) TTDAB (c) Tm-MTDAB

9 Table S2 Pore and surface properties of TTPPA, TTDAB and Tm-MTDAB. TCMPs S BET a S Langmuir a V total V micro c V micro / S micro c S external c (m 2 g -1 ) (m 2 g -1 ) (tpv) b (cm 3 g -1 ) V total (m 2 g -1 ) (m 2 g -1 ) (cm 3 g -1 ) PTPPA TTDAB Tm-MTDAB a Specific surface area calculated from the adsorption branch of the nitrogen isotherm using the BET method in the relative pressure (P/P ) range from.1 to.1. b Total pore volume is obtained from BET data up to P/P =.97 and is defined as the sum of micropore volume and volumes of larger pores. c Micropore volume calculated from nitrogen adsorption isotherm using the t-plot method. Table S 3. Summary of surface area and iodine sorption properties of CMPs. Sample BET T ( o C) Iodine uptake Ref (heteroatom) (m 2 g -1 ) (g g -1 ) NiP-CMPs Chem. Commun. 214, 5, (N) PAF-1, JUC-Z2 56, , 1.44 J. Mater. Chem. A, 214, 2, (no N, S) CMPN-1,CMPN-2, , 1.1, J. Mater. Chem. A, 215, 3, 87

10 CMPN-3 (no N, S) PAF-23, PAF-24, 82, 136, , 2.76, Angew. Chem. Int. Ed., 215, PAF-25 (B, Li + ) , Azo-Trip Polym. Chem., 216, 7, 643 (N) 647. SCMP-1, SCMP-2 413, , 2.22 ACS Appl. Mater. Interfaces, (S) 216, 8, SCMP-I, SCMP-II 2.72, Chem. Commun., 216, 52, (S) Por-Py-CMP RSC Adv., 216, 6, (N) HCMP-1, -2, -3, -4 43, 153, , 2.81, Macromolecules, 216, 49, (N) 82, n.a. 3.16, NTP ACS Macro Lett., 216, 5, (N) N APOP-1,-2,-3,-4 657, 458, ,2.39, J. Polym. Sci., Part A: Polym. (N) 72, ,2.65 Chem. 216, 54, COP 1 ++, COP 1.+, , 1.95, J. Mater. Chem. A, 216, 4(4): COP 1,COP 2 ++, 3.8,2.58, COP 2.+, COP 2 (N) 2.11,2.77 BQCMP-1, Macromol. Mater. Eng. 216, BQCMP-2 (N) ,

11 AzoPPN (N) Chem. Eur. J., 216, 22(33), POP-1,POP-2 12, , 3.82 J. Hazard. Mater. 217, 338, (N) TTPB (N) J. Mater. Chem. A, 217, 5, FCMP-6@ , 636, , 1.41 Sci Rep, 217, 7(1): (F) 692, 88.9, NCMP1, NCMP2, 58, 28, , 1.86, ACS Appl. Mater. Interfaces, NCMP3 (N) , TTPPA(N) This work. TTDTPA(N) This work. TTMTPA(N) This work. Fig. S6. Photographs showing the color changes before and after iodine capture for TTPPA, TTDAB, and Tm-MTDAB.

12 @TTPPA Theta/degree Fig. S7. XRD patterns @Tm-MTDAB Abs Fig. S8. UV Vis @Tm-MTDAB, and. Table S4. The peak shifts of FT-IR spectra of parents and iodine-loaded TCMPs shift triazine, C=N

13 triazine, C-N C-N triazine, benzene ring: in-plane triazine, benzene ring: out-ofplane H 2 O TTDAB peak shift triazine, C=N triazine, benzene ring: in-plane triazine, C-N C-N triazine, benzene ring: out-ofplane H 2 O peak shift triazine, C=N triazine, C-N triazine, benzene ring: in-plane C-N triazine, benzene ring: out-ofplane H 2 O

14 Iodine uptaking percentage (%) (a) Iodine uptaking percentage (%) Recycling percentage (%) Recycling percentage Recycling percentage (%) Iodine uptaking percentage (%) (b) Iodine uptaking percentage (%) Recycling percentage (%) Recycling percentage Recycling percentage (%) Iodine uptaking percentage (%) (c) Iodine uptaking percentage (%) Recycling percentage (%) Recycling percentage Recycling percentage (%) Fig. S 9. Recycling percentage of (a) TTPPA, (b) TTDAB and (c) Tm-MTDAB (recycling parameters: 1. bar, 35 K, 22 h and 398 k, 12 min).

15 Abs (a) 2.25 mg L mg L mg L mg L -1 1 mg L -1 2 mg L -1 4 mg L -1 3 mg L -1 5 mg L Abs (b) R 2 = Concentration (mg L -1 ) Fig. S1. (a) Calibration plot of standard iodine by UV-Vis spectra in cyclohexane solution. (b) The fitting of Abs value vs concentration of with the relatively good linearity satisfies Lambert-Beer Law.

16 (a) Wavenumber (cm -1 ) TTPPA cyclohexane TTDAB Wavenumber (cm -1 ) cyclohexane Wavenumber (cm -1 ) Tm-MTDAB Fig. S11. Raman spectra of iodine cyclohexane solution (black), iodine-loaded TCMPs obtained by iodine sorption in cyclohexane solution (red) and TCMPs (green); (a) TTPPA, (b) TTDAB and (c) Tm-MTDAB.

17 Fig. S12. Photographs showing progress of the iodine release from and respectively, when the containing iodine polymer networks were immersed in ethanol (a) Abs mg L -1 2 mg L -1 4 mg L -1 5 mg L

18 Abs (b) R 2 = Concentration (mg L -1 ) Fig. S13. (a) Calibration plot of standard iodine by UV-Vis spectra in ethanol solution. (b) The fitting of Abs value vs concentration of with the relatively good linearitysatisfies Lambert-Beer Law. 7 Release percentage (%) Release @Tm-MTDAB Fig. S14. Controlled release rate of iodine in TTPPA, TTDAB and Tm-MTDAB in the first 3 min determined by UV Vis absorbance at 291 nm.

19 Fluorescence Intensity (a.u.) (a) DMF DOX Chloroform EtOH ACN Acetone THF Fluorescence Intensity (a.u.) (b) ACN Acetone DMF DOX Chloroform THF Ethanol Fluorescence Intensity (a.u.) 2 (c) ACN Acetone DMF DOX Chloroform THF EtOH Fig. S15. Fluorescence emission spectra of (a) TTPPA, (b) TTDAB, and (c) Tm- MTDAB suspended in varying polar solvent: ACN, acetone, DMF, DOX, chloroform, THF, and ethanol, respectively, excited with the wavelength of 34, 34 and 35 nm, respectively.

20 Fig. S16. Luminescence photographs of dispersions of (a) TTPPA, (b)ttdab, and (c) Tm-MTDAB in different solvents under UV irradiation at λex=365 nm. Fluorescence Intensity (a.u.) (a) TTPPA-THF (TTPPA+o-NP)2s 4s 6s 8s 1s 12s 14s 16s 18s

21 Fluorescence Intensity (a.u.) (b) TTDAB-DOX (TTDAB+o-NP)14s 12s 1s 6s 4s 2s Fluorescence Intensity (a.u.) 125 (c) (Tm-MTDAB+o-NP)14s Tm-MTDAB-THF 4s 2s 12s 1s 8s 6s Fluorescence Intensity (a.u.) (d) Time (s) TTPPA TTDAB Tm-MTDAB Fig. S17. Fluorescence spectral changes of (a) TTPPA, (b) TTDAB, and (c) Tm- MTDAB upon addition of o-np of mol L -1 with time. (d) The curves are the

22 evolution of maximum photoluminescence intensity as a function of time. The excitation wavelength was 34, 34 and 35 nm, respectively. 35 (a) o-np I /I NB PA DClB NT DNT PhOH [A]*1-4 mol L -1 I /I (b) o-np DNT NT NB PA PhOH [A]*1-4 mol L -1

23 I /I (c) o-np DNT NT NB PA PhOH DClB [A]*1-4 mol L -1 Fig. S18. The plots of I /I against varying NACs concentrations. Polymer concentrations: 1. mg L -1. (a) TTPPA in THF (λex=34 nm ), (b) TTDAB in DOX (λex=34 nm), (c) Tm-MTDAB in THF ( λex=35 nm). Table S4. The equation of I /I of TTPPA, TTDAB and Tm-MTDAB to the concentrations of o-np for suspension in THF or DOX. CMPs Solvent The equation Regression The concentration detection coefficient range of PA limit (R) (mol L -1 ) (mol L -1 ) TTPPA THF I /I= [o-np].9972 to TTDAB DOX I /I= [o-np].9995 to Tm-MTDAB THF I /I= [o-np].9969 to

24 (a) Free or TTPPA+NACs TTPPA+o-NP+NACs 1 I /I I /I Free (b) Free (c) o-np NP NB PA PA DClB NT DNT NT Tm-MTDAB+NACs Tm-MTDAB+o-NP+NACs DNT PhOH TTDAB+NACs TTDAB+o-NP+NACs NB PhOH I /I Free NP DNT NT DClB NB PA PhOH Fig. S19. The PL quenching of three TCMPs for sensing NACs at the same concentration of mol L -1 in THF or DOX solutions. (a) TTPPA, (b) TTDAB, and (c) Tm-MTDAB.

25 Fluorescence Intensity (a.u.) Fluorescence Intensity (a.u.) Fluorescence Intensity (a.u.) (a) r.t. 5 o C 1 o C 15 o C 2 o C (b) (c) r.t. 5 o C 1 o C 15 o C 2 o C r.t. 5 o C 1 o C 15 o C 2 o C Fig. S2. Fluorescent spectra of (a) TTPPA (λex=34 nm ), (b) TTDAB (λex=34 nm), and (c) Tm-MTDAB( λex=35 nm) before and after annealing at different temperatures for 3 min in air.