Electronic Supporting Information

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1 Electronic Supporting Information Highly Efficient and Reversible Iodine Capture in Hexaphenylbenzene-Based Conjugated Microporous Polymers Yaozu Liao,,*, Jens Weber, Ben Mills, Zihao Ren, and Charl F. J. Faul,* State Key Laboratory for Modification of Chemical Fibers and Polymer Materials & College of Materials Science and Engineering, Donghua University, Shanghai , P. R. China School of Chemistry, University of Bristol, Bristol, England BS8 1TS, UK Department of Chemistry, Hochschule Zittau/Görlitz (University of Applied Science), Theodor-Körner-Allee 16, D Zittau, Germany Corresponding authors: Figure S1 Toroidal delocalization of charge in hexaphenylbenzene. 1 Figure S2 Appearance of HCMP-1 (brown), 2 (dark-blue), 3 (yellow) and 4 (dark- brown) solids. 1

2 HBB Intensity /a.u. HCMP-1 HCMP-2 HCMP-3 HCMP Theta /Degree Figure S3 XRD patterns of HBB and HCMPs. Figure S4 TEM/EDX spectra of HCMP-1, 2, 3 and 4 acquired by directly EDX the black dots when high-magnified TEM images were obtained. Inset values indicating the palladium (Pd) content obtained by elemental analyses. 100 Weight /% HCMP-1 HCMP-2 HCMP-3 HCMP Temperature / o C Figure S5 TGA scans of HCMPs in nitrogen. 2

3 Figure S6 Plot of CO 2 uptake measured at 273 K and 1 bar versus apparent BET surface area, as calculated from N 2 sorption at 77 K, for a range of CMPs previously reported. Figure S7 CO 2 adsorption/desorption isotherm at 303 K. Figure S8 CO 2 and N 2 adsorption/desorption experimental isotherms (symbols, single gas) at 303 K on HCMP-1 and 2 together with the respective fit functions used for IAST calculations (lines). IAST analysis was performed based on fit parameters obtained from analysis of single gas isotherms. The calculation was based on the assumption of a gas composition of 15% (v/v) CO 2 balanced with N 2. 3

4 Figure S9 IAST selectivity ( ) of CO 2 over N 2 (0.15/0.85 v/v gas mixture of CO 2 and N 2 ) at 303 K. (a) V ads /cm 3 g -1 STP 250 HCMP-1 HCMP K (b) V ads /cm 3 g -1 STP 60 Reduced HCMP-1 Re-oxidized HCMP-1 50 Reduced HCMP K Relative pressure p/p 0 Pressure / mmhg Figure S10 (a) N 2 and (b) CO 2 adsorption isotherms of reduced HCMP-1 and HCMP-3 as well as re-oxidized HCMP-1. Supporting information for IAST selectivity calculations: Adsorption/Desorption data was fitted using the non-linear regression tool within the qtiplot software (version rc11). The used formulas are given below. p is the pressure given in mmhg, V ads is the adsorbed amount of gas in cm³/g STP, a and b are 4

5 Langmuir-type affinity constants, q and u represent the Langmuir-type adsorption capacity: The dual-site model was used for CO 2 adsorption data, as the standard Langmuir model failed to provide an excellent analytical description of the data within the range of interest. V ads = (q*a*p/(1+a*p))+(u*b*p/(1+b*p)) (dual-site Langmuir-model) V ads = (q*a*p/(1+a*p)) (Standard Langmuir-model) Dual-site fit parameters of the CO 2 adsorption/desorption data at 303 K: q a u b HCMP HCMP Standard Langmuir fit parameters of the N 2 adsorption/desorption data at 303 K: q a HCMP HCMP Figure S11 Appearance changes of HCMP-3 upon iodine capture for 0-45 min. 5

6 Figure S12 Pseudo-second order kinetic model of iodine uptake of HCMPs as a function of time at K and ambient pressure. 0 min Iodine Intensity /a.u. 5 min 10 min 30 min 45 min Wavenumber /cm-1 Figure S13 Enlarged FT-IR spectra of iodine, HCMP-3, and iodine-loaded HCMP-3 with different time of iodine vapor exposure. 6

7 (a) (b) Intensity /a.u. Iodine HCMP-1 Iodine-loaded HCMP-1 Intensity /a.u. Iodine HCMP-2 Iodine-loaded HCMP-2 (c) Magnetic field /G (d) Magnetic field /G Intensity /a.u. Iodine HCMP-3 Iodine-loaded HCMP-3 Intensity /a.u. Iodine HCMP-4 Iodine-loaded HCMP Magnetic field /G Magnetic field /G Figure S14 ESR spectra of iodine, HCMPs and iodine-loaded HCMPs for 45 min: (a) HCMP-1, (b) HCMP-2, (c) HCMP-3 and (d) HCMP-4. I 3d5/2 Inensity / a.u ev ev Binding energy / ev Figure S15 I 3d5/2 XPS spectrum of iodine-loaded HCMP-3. 7

8 Figure S16 TD-DFT-calculated UV-Vis/NIR spectra of the reduced (pristine) states of HCMP-1, 2, 3 and 4. Figure S17 TD-DFT-calculated UV-vis/NIR spectra of the oxidised (quinoidal) states of HCMP-1, 2, 3 and 4. 8

9 Absorbence /a.u. HCMP-1 HCMP-2 HCMP-4 HCMP Wavelength /nm Figure S18 UV-vis/NIR spectra of iodine-loaded HCMP-1, 2, 3 and 4 with 45 min of iodine vapor exposure. Figure S19 TD-DFT-calculated UV-Vis/NIR spectra of the radical cationic states of HCMP-1, 2, 3 and 4. 9

10 (a) Abs. (c) Abs Iodine release time /min Wavelength /nm Iodine release time /min Wavelength /nm (b) Abs. 2 Iodine release time /min 1 0 (d) Abs Wavelength /nm Iodine release time /min Wavelength /nm Figure S20 Temporal evolution of UV-vis absorption spectra of the iodine released from loaded (a) HCMP-1, (b) HCMP-2, (c) HCMP-3 and (d) HCMP-4 in 3.5 ml of ethanol. Figure S21 Pictures showing iodine (a) uptake, (b) release in ethanol and (c) release upon heating. 10

11 Table S1 Summary of structures, BET surface areas and CO 2 uptakes (273 k, 1 bar) of CMPs CMPs Chemical structure Surface area CO 2 uptake Symb. Ref. (m 2 g -1 ) (mmol g -1 ) HCMP This work CMP CMP TCMP TFM COF COF COF COF

12 COF CMP CMP (OH) 2 CMP (CH 3 ) 2 CMP NH 2 CMP-1- COOH Tet G ACMP-C PI PTPA

13 Adsorbents Table S2 Summary of S BET and iodine uptake properties of porous materials series. S BET (m 2 g -1 ) Pressure T (K) a Eq. time Iodine uptake (wt%) c HCMP bar min 159 This work HCMP bar min 281 This work HCMP bar min 316 This work HCMP-4 n.a. 1 bar min 222 This work NiP-CMP bar h CMPN bar h CMPN bar h CMPN bar h PFA Pa h JUC-Z Pa h ZIF bar h Amorphized ZIF-8-1 bar min Ref HKUST bar PU1-1 bar d Ag@Mon-POF bar Ag@Zeolite Mordenites - 1 bar h {[Cd(L) 2 (Cl - 1 bar O 4 ) 2 ]H 2 O} n CC3-1 bar h TPP - 1 bar TPP - 1 bar Mesitylene b {[Zn 3 (DL-lac) 2 (pybz) 2 ] n {[Cu 6 (pybz) 8 (OH) 2 ]} n bar 273 Cyclohexane b c H 2 O 40 h h {[Cu 6 (pybz) 8 (OH) 2 ]} n c H 2 O 72 h NiMoS chalcogels bar d a: If no specification was indicated, iodine was adsorbed via vapor trapping; b: iodine was adsorbed in solvent; b: iodine was sublimated via hydrothermal synthesis; c: wt% = iodine mass/adsorbent mass. 13

14 Table S3 Kinetic data of the iodine adsorption of HCMPs. HCMP slope y-intercept q eq [g/g] k [g/(g*min)] R Used equation: t q t = 1 k q e q e t where q t is the adsorbed amount at time t, q e is the equilibrium uptake and k is the adsorption rate constant. y-intercept is equal to 1/(k*q e ²) and the slope is equal to 1/q e. Table S4 Structures of the fragments used to model the UV/vis/NIR spectra of HCMPs 1-4. HCMP Linker Model fragment HOMO energy / ev 1 1,4-diaminobenzene ,4 -diaminodiphenylamine o-tolidine ,4 -diaminostilbene

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