Supporting Information

Supporting Information

Porphyrin-Based Conjugated Microporous Polymer

Tubes: Template-Free Synthesis and A Photocatalyst for

Visible-Light-Driven Thiocyanation of Anilines

Pengfei Zhang,a Yucheng Yin,a Zhengxin Wang,b Chunyang Yu,a Yizhou Zhu,c Deyue Yan,a Weimin Liu,b and Yiyong Mai*a

a

School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China. *E-mail: [email protected]

b

School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Road, Shanghai 201210, China.

c

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.

Table of Contents

1. Materials and measurements ... S2 2. Synthesis of CMPs ... S5 3. General procedure for thiocyanation of anilines ... S11 4. Supplementary figures and tables ... S16

5. 1H NMR and 13C NMR spectra of thiocyanated anilines (8) ... S36 6. Reference. ... S61

1. Materials and measurements

Commercial reagents were purchased from Adamas-beta® Sigma, Aldrich, Alfa and TCI and used without further purification. All solvents were purified by drying with anhydrous calcium sulfate, followed by distillation under reduced pressure. CDCl3 was purchased from Adamas-beta®Sigma.

Flash chromatography was carried out on Merck 60 silica gel (100-200 mesh).

1

H and 13C NMR spectra were recorded with Bruker (400 MHz) spectrometer. All

the 1H NMR and 13C NMR spectra were measured in the CDCl3. 1H NMR spectra

were referenced to TMS (0 ppm), and reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet). Chemical shifts of 13C NMR spectra were referenced to CDCl3 (78.0 ppm).

All solid-state NMR experiments were conducted on a Bruker Avance NEO 500 spectrometer (νL(1H) = 500 MHz, 11.74 T) using a Bruker 1.3 mm DVT H/F/X/Y

probe. The samples were packed in ZrO2 with an o.d. of 1.3 mm and sealed with

Vespel© bottom and top caps. Adamantane was used as external reference to calibrate the radiofrequency (rf) field strength and chemical shift scale (δ(1H) = 1.85 ppm).

Mass spectral data were obtained by matrix-assisted laser

decomposition/ionization time of flight mass spectrometry (MALDI-TOF) using 7,7,8,8-tetracyanoquinodimethane (TCNQ) as matrix on a Bruker Reflex II-TOF spectrometer. All experiments were performed at room temperature. The theoretical molecular weights of the compounds were calculated by the Bruker Compass Data analysis software.

Fourier transform infrared (FTIR) spectra were recorded on a Spectrum 100

(Perkin Elmer, Inc., USA) spectrometer.

Inductively coupled plasma mass (ICP MS) were conducted on a thermo fisher

instrument (Germany).

Optical microscope observations were performed on a TOM/LEICA DM 4000

Sirion-200 (FEI Co., USA) field emission scanning electron microscope at 10 kV.

Transmission electron microscopy (TEM) measurements were performed on a

JEOL-2100 (JEOL Ltd., Japan) at an accelerating voltage of 200 kV. Nitrogen adsorption-desorption isotherms were measured at 77K on an Autosorb-iQA3200-4 sorption analyzer (Quantatech Co., USA) instrument. Before measurement, the samples were degassed in a vacuum at 150 °C for at least six hours.

Brunauer-Emmett-Teller (BET) method was utilized to calculate the specific

surface area using adsorption data in a relative pressure range from 0.06 to 0.2. The pore size distributions were derived from the adsorption branches of isotherms using the Barrett-Joyner-Halenda (BJH) method.

The UV/vis absorption spectra were recorded using a JASCO V-630

spectrophotometer.

Fluorescence emission spectra were recorded on an FLS1000/FLS1000 steady

state transient fluorescence spectrometer.

The pump-probe nanosecond transient absorption spectra were obtained using

an EOS Fire Nanosecond Transient Absorption Spectrometer (Ultrafast Systems). The white-light continuum probe pulses (350-950 nm) come from a sub-nanosecond pulsed probe light source-a PCF (photonic crystal fiber) based supercontinuum laser. 7 mJ, 1 kHz, 800 nm fundament pulses were obtained from Astrella Integrated Ti:S Amplifier (Coherent, Inc.) with -38 fs width duration (full width at half-maximum, fwhm).

Photocurrent measurement was carried out using a CH instrument model CHI600 potentiostat.

The intensity of light in the photocatalysis was measured by a PL-MW 2000

Photoradiometer. The distance between the white LED and the photoradiometer was 5 cm, and the intensity was measured to be 16.1 ± 0.1 mW cm−2.

X-ray single diffraction analysis was obtained using single crystal X-ray

diffractometer (*/D8 VENTURE).

spectrometer.

The Mott-Schottky analysis was performed on a CHI760E electrochemical

workstation at room temperature in the dark.Glassy carbon electrode, platinum wire electrode and saturated calomel electrode (SCE) are used as working electrode, assistant electrode and reference electrode respectively. The Mott-Schottky measurement was carried out in 0.1 M Na2SO4 aqueous solution at frequency of 1000

Hz. The electrochemical impedance spectra were obtained by immersing in a 0.1 M Na2SO4 aqueous solution.

2. Synthesis of CMPs

The porphyrin-based CMP tubes (Scheme 1 in the main text) were prepared via the modification of a reported procedure1 (see Scheme S1).

Scheme S1. Synthesis of the porphyrin-based CMPs.

Dipyrromethane

First of all, dipyrromethane was synthesized. Briefly, formaldehyde (37% aqueous, 20 g, 0.25 mol) was added to pyrrole (85 g, 1.25 mol). Then, Indium (III) chloride (370 mg, 1.67 mmol) was added and the mixture was stirred at room temperature for 10 minutes under argon atmosphere. Then, the mixture was stirred at 55 °C for another 6 hours. Afterwards, sodium hydroxide (NaOH, 0.2 g, 83.5 mmol) was added and stirred for 4 hours and then the mixture was filtered. The filtrate was concentrated, and the residue was subjected to silica-gel column chromatography using hexane: ethyl acetate = 8: 1 (v/v) and then dried to give 7.5 g white solid (yield: 20%).

1

H NMR (400 MHz, CDCl3): δ = 7.47 (brs, 2H), 6.62 (dd, 2H), 6.21 (dd, 2H), 6.09 (s,

2H), 3.95 (s, 2H).

13

5,15-diundecylporphyrin

5,15-diundecylporphyrin 3-1 was prepared by the modification of a reported procedure2. Briefly, a solution of meso-free dipyrromethane (1.07 g, 7.43 mmol) and dodecyl aldehyde (1.26 g, 7.38 mmol) in CH2Cl2 (1.4 L) was bubbled by using argon

for 5 min in a 2 L round-bottom flask, to which was added trifluoroacetic acid (0.055 mL, 0.743 mmol). The mixture was stirred overnight at room temperature and then 2,3-dicyano-5,6-dichlorobenzoquinone (2.54 g, 11.2 mmol) was added. The mixture was stirred for another 1 hour, and then quenched with triethylamine and filtered through a short alumina column. The solvent was removed and the residue was purified by silica-gel column chromatography with CH2Cl2 as the eluent. Finally, the

product was dried to give 5,15-dihexyl substituted porphyrin in a 42% yield (700 mg).

1 H NMR (400 MHz, CDCl3): δ= -2.92 (br s, 2H), 0.86-0.89 (m, 6H), 1.27-1.48 (m, 22H), 1.50-1.54 (m, 8H), 1.80-1.83 (m, 4H), 2.52-2.56 (m, 4H), 4.97-5.01 (m, 4H), 9.39-9.40 (d, 4H), 9.56-9.57 (d, 4H), and 10.15 (s, 2H); 13 C NMR (100 MHz; CDCl3): δ = 147.67, 144.39, 132.07, 128.02, 119.06, 104.46, 38.89, 34.87, 32.14, 30.83, 29.94, 29.87, 29.57, 22.92, 14.35.

5,15-bis(4-dodecylphenyl)porphyrin

Similar to 3-1, 5,15-bis(4-dodecylphenyl)porphyrin 3-2 was sythesized by the modification of a reported procedure2. Briefly, a solution of meso-free dipyrromethane (1.07 g, 7.43 mmol) and 4-dodecylbenzaldehyde (2.0 g, 7.38 mmol) in CH2Cl2 (1.4 L) was bubbled by nitrogen for 5 min in a 2L round-bottom flask, to

which was added trifluoroacetic acid (0.055 mL, 0.743 mmol). The mixture was stirred overnight at room temperature and then 2,3-dicyano-5,6-dichlorobenzoquinone (2.54 g, 11.2 mmol) was added. The mixture was stirred for one more hour, and then quenched with triethylamine and filtered through a short alumina column. The solvent was removed and the residue was purified by silica-gel column chromatography with CH2Cl2 as the eluent. Finally, the product was dried to give 5,15-dihexyl substituted

porphyrin in a 38% yield (880 mg). 1 H NMR (400 MHz, CDCl3): δ= -3.06 (br s, 2H), 0.95-1.01 (m, 6H), 1.29-1.39 (m, 24H), 1.49-1.53 (m, 12H), 1.91 (m, 8H), 7.59-7.61 (d, 4H), 8.20-8.22 (d, 4H), 9.15-9.18 (d, 4H), 9.40-9.45 (d, 4H), and 10.34 (s, 2H); 13 C NMR (100 MHz; CDCl3): δ = 147.58, 146.20, 145.32, 138.92, 135.04, 131.65, 131.38, 126.52, 119.61, 105.34, 70.77, 46.36, 37.45, 32.23, 29.97, 29.66, 28.15, 27.83, 23.01, 14.45.

5,15-dibromo-10,20-diundecylporphyrin

To a solution of 5,15-diundecylporphyrin 3-1 (309.6 mg, 0.5 mmol) in dichloromethane (50 mL) and methanol (10 mL) was added N-bromosuccinimide (NBS) (214.0 mg, 1.2 mmol). After stirring for 20 min at room temperature, acetone (5 mL) was added to quench the reaction, and then the solvents were evaporated. The residue was dissolved in dichloromethane (100 mL) and passed through a silica gel column (eluent: dichloromethane). After concentration, the residue was recrystallized from the mixed solvent of dichloromethane and methanol to give a purple solid (370.7 mg, 96% yield). 1 H NMR (400 MHz, CDCl3): δ=-0.33 (br s, 2H), 0.78-0.81 (m, 6H), 1.23-1.40 (m, 20H), 1.51-1.61(m, 8H) 2.15-2.22 (m, 8H), 4.33-4.37 (m, 4H), 9.15-9.17 (d, 4H), 9.35-9.36 (d, 4H). 13 C NMR (100 MHz; CDCl3): δ = 157.56, 154.24, 132.07, 124.02, 119.06, 104.35, 38.87, 34.57, 32.92, 30.83, 29.94, 29.89, 29.87, 22.14, 14.35.

5,15-dibromo-10,20-bis(4-dodecylphenyl)porphyrin

To a solution of 5,15-diundecylporphyrin 3-2 (399.6 mg, 0.5 mmol) in dichloromethane (50 mL) and methanol (10 mL) was added N-bromosuccinimide (NBS) (214.0 mg, 1.2 mmol). After stirring for 20 min at room temperature, acetone (5 mL) was added to quench the reaction, and then the solvents were evaporated. The residue was dissolved in dichloromethane (100 mL) and passed through a silica gel column (eluent: dichloromethane). After concentration, the residue was recrystallized from the mixed solvent of dichloromethane and methanol to give a purple solid (456.7 mg, 95% yield). 1 H NMR (400 MHz, CDCl3): δ= -2.73 (br s, 2H), 0.98-1.11 (m, 6H), 1.39-1.47 (m, 36H), 1.89-2.07 (m, 8H), 7.53-7.55 (d, 4H), 8.05-8.07 (d, 4H), 8.87-8.89 (d, 4H) and 9.60-9.62 (d, 4H). 13 C NMR (100 MHz; CDCl3): δ = 148.07, 146.61, 138.87, 134.75, 132.33, 126.33, 125.67, 121.91, 103.82, 48.16, 46.36 40.21, 39.68, 38.97, 37.38, 32.36, 32.23, 28.14, 23.22, 21.29, 14.45, 12.76.

HRMS (MALDI+) m/z: calcd. for C42H56Br2N4 (M)+: 956.2760; found:956.2790.

Synthesis of CMPs

A 50 mL Schlenk tube was flame-dried. Under nitrogen, brominated porphyrins 4 (1.2 mmol) and 4,4''-diethynyl-5'-(4-ethynylphenyl)-1,1',3',1''-terphenyl 5 (0.302g,

0.80 mmol) were dissolved in a mixture of tetrahydrofuran (5 mL) and triethylamine (5 mL). Then, bis(triphenylphosphine)palladium dichloride (14 mg, 0.020mmol) and copper iodide (2.0 mg, 0.010 mmol) were added to the solution. The reaction mixture was stirred at 90 oC for 3 days under nitrogen to ensure the complete conversion of all the monomers. During the reaction, yellow precipitate was gradually formed in the reaction mixture. After the solution was cooled to room temperature, the resultant black precipitate was isolated by centrifugation. After being washed with excess methanol, dichloromethane, diethyl ether and toluene, the product was dried under vacuum for one day.

3. General procedures for thiocyanation of anilines

All reactions were carried out in an over-dried 10 mL Schlenk tube equipped with a stir bar. All solvents were dried and distilled before use.

CMPs (15 wt %) was added to a solution of aniline 6 (0.5 mmol) and ammonium

thiocyanate 7 (1.5 mmol) in organic solvent (5 mL) under oxygen or air atmosphere. The reaction mixture was sonicated for 1 minute. Then the mixture was stirred under a 18 W LED (white light, the distance between LED and Schlenk tube is 5 cm) irradiation at room temperature. After the reaction, the reaction mixture was diluted with dichloromethane (15 mL) and then silica gel powder (5 g, 100-200 mesh) was added. After the removal of the solvent under reduced pressure, the crude product was purified by silica-gel column chromatography with petroleum ether/ethyl acetate (3:1-10:1, v/v) to give the final 4-thiocyanated anilines 8.

N,N-Dimethyl-4-thiocyanatoaniline (8a)

Yellow solid (91%, yield). 1H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 7.7 Hz, 2H),

6.60 (d, J = 7.9 Hz, 2H), 2.92 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 151.69, 134.52,

113.14, 112.66, 106.49, 40.16. HRMS (ESI-TOF) m/z [M+H]+

calcad for C9H11N2S

179.0637, found179.0640.

N,N,3-Trimethyl-4-thiocyanatoaniline (8b)

Yellow solid. (85%, yield). 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 11.2 Hz, 1H),

6.59 (s, 1H), 6.52 (dd, J = 8.7, 2.8 Hz, 1H), 3.00 (s, 6H), 2.51 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 152.26, 142.64, 136.15, 114.33, 110.94, 40.14, 21.48. HRMS

(ESI-TOF) m/z [M+H]+ calcad for C10H13N2S 193.0794, found193.0792. N,N,2-Trimethyl-4-thiocyanatoaniline (8c)

Yellow solid (87%, yield). 1H NMR (400 MHz, CDCl3) δ 7.43 (dd, J = 11.3 Hz, 1H),

6.58 (s, 1H), 6.52 (d, J = 8.8, 2.6 Hz, 1H), 3.08 (s, 6H), 2.51 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 152.26, 142.64, 136.15, 114.33, 110.94, 40.14, 21.48. HRMS

(ESI-TOF) m/z [M+H]+ calcad for C10H13N2S 193.0794, found193.0794. N,N,3,5-Tetramethyl-4-thiocyanatoaniline (8d)

White solid (50%, yield). 1H NMR (400 MHz, CDCl3) δ 6.47 (s, 2H), 2.97 (s, 6H),

2.54 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 151.18, 144.33, 112.49, 107.4, 99.97,

30.19, 22.26. HRMS (ESI-TOF) m/z [M+H]+

2-Chloro-N,N-dimethyl-4-thiocyanatoaniline (8e)

White solid (74%, yield). 1H NMR (400 MHz, CDCl3) δ 7.42 (J = 11.7Hz, 1H), 6.58

(d,), 6.52 (d, J = 8.7, 2.6 Hz, 1H), 3.08 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 152.27,

142.64, 136.15, 126.25, 114.33, 110.94, 106.37, 40.14. HRMS (ESI-TOF) m/z [M+H]+ calcad for C9H10ClN2S 213.0175, found213.0172.

N,N-Diethyl-4-thiocyanatoaniline (8f)

Yellow solid (90%, yield). 1H NMR (400 MHz, CDCl3) δ 7.42 (d, 2H), 6.66 (d, 2H),

3.37-3.42 (q, J = 7.1 Hz, 4H), 1.18-1.22 (t, 6H). 13C NMR (100 MHz, CDCl3) δ

149.29, 135.02, 112.85, 112.57, 104.96, 44.49, 12.35. HRMS (ESI-TOF) m/z [M+H]+

calcad for C13H19N2S 207.0950, found 207.0952. N,N-Dipropyl-4-thiocyanatoaniline (8g)

White solid (79%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 9.0 Hz, 2H),

6.61 (d, J = 12.2 Hz, 2H), 3.22–3.26 (m, 4H), 1.55-1.65 (m, 4H), 0.91-0.95 (t, J = 9.6, 5.2 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 149.72, 134.93, 112.85, 112.66, 104.84,

52.77, 20.20, 11.37. HRMS (ESI-TOF) m/z [M+H]+ calcad for C13H19N2S 235.1263,

found 235.1262.

1-(4-Thiocyanatophenyl) piperidine (8h)

White solid (82%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 8.5 Hz, 2H),

6.90–6.93 (d, J = 10.2 Hz, 2H), 3.26–3.29 (m, 4H), 1.65–1.71 (m, 6H). 13C NMR (100 MHz, CDCl3) δ 153.03, 134.04, 116.46, 112.31, 109.06, 49.22, 25.36, 24.22. HRMS

(ESI-TOF) m/z [M+H]+ calcad for C12H15N2S 219.0950, found 219.0951.

4-(4-Thiocyanatophenyl)morpholine (8i)

Yellow solid (92%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 16.8 Hz, 2H),

6.91 (d, J = 21.9 Hz, 2H), 3.85–3.88 (m, 4H), 3.21–3.24 (m, 4H). 13C NMR (100 MHz, CDCl3) δ 152.55, 133.76, 116.19, 111.95, 111.17, 66.57, 48.06. HRMS

(ESI-TOF) m/z [M+H]+ calcad for C11H13N2OS 221.0743, found 221.0748.

2-(Ethyl(4-thiocyanatophenyl)amino)ethan-1-ol (8j)

Red solid (43%, yield). 1H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 8.9 Hz, 2H), 6.74

(d, J = 8.9 Hz, 2H), 3.81 (t, J = 5.9 Hz, 2H), 3.43-3.52 (m, 5.6 Hz, 4H), 1.19 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 149.79, 134.83, 129.32, 113.19, 106.29,

60.01, 52.21, 45.53, 11.72. HRMS (ESI-TOF) m/z [M+H]+ calcad for C11H15N2OS

223.0900, found 223.0642.

4H), 7.28–7.22 (t, 1H), 7.18 (d, J = 7.4 Hz, 2H), 6.70–6.61 (d, J = 8.4 Hz, 2H), 4.54 (s, 2H), 3.50 (q, J = 7.1 Hz, 2H), 1.22 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ

150.00, 137.76, 134.88, 128.83, 127.19, 126.27, 113.15, 112.73, 106.21, 53.75, 45.58, 12.06. HRMS (ESI-TOF) m/z [M+H]+ calcad for C16H17N2S 269.1107, found

269.1110.

N-Methyl-4-thiocyanatoaniline (8l)

White solid (79%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 9.7 Hz, 2H),

6.58 (d, J = 8.4 Hz, 2H), 2.84 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 151.10, 134.77,

113.39, 112.68, 107.50, 30.26. HRMS (ESI-TOF) m/z [M+H]+ calcad for C8H9N2S

165.0481, found 165.0481.

N,2-Dimethyl-4-thiocyanatoaniline (8m)

Red solid (70%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.5 Hz, 1H), 7.28

(s, 1H), 6.58 (d, J = 8.5 Hz, 2H), 3.94 (s, 1H), 2.92 (d, J = 9.6 Hz, 3H), 2.14 (s, 3H).

13

C NMR (100 MHz, CDCl3) δ 165.32, 149.20, 134.56, 132.91, 123.61, 112.87,

109.91, 106.92, 30.43, 17.21. HRMS (ESI-TOF) m/z [M+H]+ calcad for C9H11N2S

179.0637, found 179.0639.

N,3-Dimethyl-4-thiocyanatoaniline (8n)

Red solid (63%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 10.7 Hz, 1H), 7.28

(s, 1H), 6.58 (d, J = 2.6 Hz, 1H), 3.94 (s, 1H) 2.92 (s, 3H), 2.14 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 149.20, 134.56, 132.91, 123.61, 112.87, 109.91, 106.92, 30.43,

17.21. HRMS (ESI-TOF) m/z [M+H]+ calcad for C9H11N2S 179.0565, found

179.0561.

3-Chloro-N-methyl-4-thiocyanatoaniline (8o)

White solid (77%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 10.7 Hz, 1H),

6.64 (s, 1H), 6.45 (dd, J = 8.7, 2.6 Hz, 1H), 4.47 (s, 1H), 2.81 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 152.27, 138.41, 135.66, 113.11, 112.17, 111.52, 106.02, 30.13.

HRMS (ESI-TOF) m/z [M+H]+ calcad for C8H8ClN2S 199.0091, found 199.0212.

2-Fluoro-N-methyl-4-thiocyanatoaniline (8p)

Red oil (82%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.27-7.29 (d, J = 12.8 Hz, 1H),

7.21-7.24 (d, J = 11.0 Hz, 1H), 6.66 (t, J = 8.6 Hz, 1H), 4.33 (s, 1H), 2.91 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 152.14, 149.71, 140.19, 130.65, 118.98, 118.78, 111.79,

29.78. HRMS (ESI-TOF) m/z [M+H]+ calcad for C8H8FN2S 183.0387, found

N-ethyl-4-thiocyanatoaniline (8q)

White solid (76%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 12.8 Hz, 2H),

6.0 (d, J = 11.4 Hz, 2H), 3.94 (s, 1H), 3.16-3.22 (m, 2H), 1.27-1.31 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 150.20, 134.83, 113.63, 112.67, 107.41, 38.06, 14.57. HRMS

(ESI-TOF) m/z [M+H]+ calcad for C9H11N2S 179.0637, found 179.0637. N-Butyl-4-thiocyanatoaniline (8r)

Yellow oil (74%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.7 Hz, 2H), 6.57

(d, J = 8.7 Hz, 2H), 3.98 (s, 1H), 3.11 (t, J = 7.0 Hz, 2H), 1.60 (dt, J = 14.7, 7.2 Hz, 2H), 1.42 (dq, J = 14.5, 7.3 Hz, 2H), 1.06-0.88 (t, 3H). 13C NMR (100 MHz, CDCl3) δ

150.35, 134.86, 113.60, 112.73, 107.13, 43.19, 31.29, 20.22, 13.87. HRMS (ESI-TOF)

m/z [M+H]+ calcad for C11H15N2S 207.0950, found 207.0952. N-Isopropyl-4-thiocyanatoaniline (8s)

Yellow solid (64%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 9.5 Hz 2H),

6.54 (d, J = 8.7 Hz 2H), 3.87 (s, 1H), 3.62 (t, J = 12.5, 6.2 Hz, 1H), 1.20 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 149.41, 134.96, 114.00, 112.82, 106.79, 44.03, 22.68

HRMS (ESI-TOF) m/z [M+H]+ calcad for C10H13N2S 193.0794, found 193.0795.

2-((4-Thiocyanatophenyl)amino)ethan-1-ol (8t)

Red solid (55%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 8.4 Hz, 2H), 6.64

(d, J = 14.0 Hz, 2H), 3.87 (t, J = 10.9, 5.6 Hz, 2H), 3.32 (t, J = 13.7, 8.5 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 150.10, 134.72, 114.09, 113.26, 112.54, 60.98, 45.43.

HRMS (ESI-TOF) m/z [M+H]+ calcad for C9H11N2OS 195.0587, found 195.0587. N-Allyl-4-thiocyanatoaniline (8u)

Yellow oil (67%, yield). 1

H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 10.5 Hz, 2H),

6.62 (d, J = 10.2 Hz, 2H), 5.80-6.04 (m, 1H), 5.21-5.32 (m, 2H), 4.21 (s, 1H), 3.81 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 149.92, 134.72, 134.18, 117.30, 116.83, 113.96,

107.90, 45.92. HRMS (ESI-TOF) m/z [M+H]+ calcad for C10H11N2S 191.0637, found

191.0636.

4-Thiocyanatoaniline (8v)

Yellow solid (50%, yield). 1H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 8.3 Hz, 2H),

6.66 (d, J = 8.2 Hz, 2H), 4.07 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 149.14, 134.60,

116.11, 112.90, 109.03. HRMS (ESI-TOF) m/z [M+H]+ calcad for C7H7N2S 151.0324,

found 151.0321.

N-Methyl-N-phenyl-4-thiocyanatoaniline (8w) 1

(m, 3H), 6.82–6.77 (m, 2H), 3.30 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 150.83, 147.50, 138.78, 133.89, 133.67, 129.92, 126.14, 125.43, 125.25, 118.18, 116.61, 112.26, 109.52, 40.28. HRMS (ESI-TOF) m/z [M+H]+ calcad for C14H13N2S 241.0794, found 241.0799. N,N-Diphenyl-4-thiocyanatoaniline (8x)

White solid (40%, yield). 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.4 Hz, 2H),

7.30 (d, J = 15.5 Hz, 4H), 7.11 (dd, J = 7.8, 5.4 Hz, 6H), 7.03 (d, J = 8.5 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 150.01, 146.65, 133.17, 129.65, 125.49, 124.38, 122.76,

113.45, 111.68, 100.00. HRMS (ESI-TOF) m/z [M+H]+ calcad for C19H15N2S

4. Supplementary figures and tables

Figure S1. 1H NMR spectrum of 3-1.

Figure S3. MALDI-TOF spectrum of 3-1. Figure S4. 1H NMR spectrum of 3-2. 477.30230 1+ 618.46407 1+ YP201970049ZPF-F_0_P2_000001.d: +MS 450 500 550 600 650 700 750 800 850 900 950 m/z 0.0 0.2 0.4 0.6 0.8 1.0 10 x10 Intens. YP201970049ZPF-F_0_P2_000001.d: +MS

Figure S5. 13C NMR spectrum of 3-2.

Figure S7. 1H NMR spectrum of 4-1.

Figure S9. MALDI-TOF spectrum of 4-1.

Figure S11. 13C NMR spectrum of 4-2.

Figure S13. FTIR spectra of 4-1 (a) and 4-2 (b).

Figure S15. Solid-state 13C NMR spectra of 4-2, 5 and CMP-2.

Figure S17. Powder XRD patterns of CMP-1 and CMP-2. 550 600 650 700 750 800 0.00E+000 2.00E+007 4.00E+007 6.00E+007 8.00E+007 1.00E+008 1.20E+008 1.40E+008 Intensity Wavelength / nm

Porphyrin 4-1

Figure S19. Differential absorption changes (visible) obtained via nanosecond

pump-probe experiments of CMP-1 ((a) and (b) are at 460 nm) and CMP-2((c) and (d) are at 440 nm) in argon saturated THF at room temperature with several time delays between 100 ps and 400 μs.

Table S1. Comparison of typical thermal catalytic methods and our photocatalytic

protocol for the thiocyanation of anilines

SCN reagent a Catalysts Temperature Time Yield Ref.

3 steps to obtain R1. 1.1 equiv None r.t. 12 h 80% J. Org. Chem. 2018, 83, 1576-1583

3 steps to obtain III.

60 mol% H2O2 as solvent r.t. 2 h 88% J. Sulfur. Chem. 2018, 39, 294-307 TMSCN Marketed 2.0 equiv S8 2.0 equiv 90 ℃ 4 h 80% Chem. Commun., 2018, 54, 13367-1337 0 2 steps to obtain [P4-VP]SCN. 2.5 equiv 2.2 equiv r.t. 2 h 80% J. Sulfur. Chem. 2016, 37, 282-295 NH4SCN Marketed 2.0 equiv 2.2 equiv 60 ℃ 4 h 90% Synlett 2016, 27, 237–240 3 steps to obtain. 1.0 equiv AuCl3 1 mol% r.t. 3 day 92% Chem. Eur. J. 2015, 21, 14324 – 14327

2 steps to obtain [P4-VP]SCN. 1.5 equiv Potassium peroxydisulfate (PPDS) 1.0 equiv 55 ℃ 2 h 88% J. Sulfur. Chem. 2014, 35, 458-469 NH4SCN Marketed 2.2 equiv HIO3 1.5 equiv r.t. 0.5 h 92% Syn. Commun. 2009, 39, 2674-2682 NaSCN Marketed 1.5 equiv Cu(ClO4)2 r.t. 10 h 82% J. Org. Chem. 2006, 71, 9849-9852 NH4SCN Marketed 3.0 equiv CMP-1 15 wt% r.t. 4 h 93% This work

Figure S22. The 1H NMR spectrum of the reaction result of 6y in the main text.

Figure S24. The 1H NMR spectrum of the reaction result of Scheme 4a in main text.

Figure S25. GC-MS results of the trapping experiments with TEMPO as shown in

Figure S26. GC-MS results of the trapping experiments with TEMPO as shown in

Scheme 4b in the main text.

Figure S27. GC-MS results of the trapping experiments with TEMPO as shown in

Computational Calculations

All calculations were carried out with the GAUSSIAN 09 package3. The recently developed b3lyp functional, together with the standard 6-31+g(d) basis set, were used for optimizing the geometry of all the minima states. All the optimized structures were confirmed by frequency calculations. To take solvent effects into account, solution-phase single-point calculations were performed on the gas-phase geometries.15 The solution-phase single point energy calculations were done using B3LYP method at a larger basis set 6-311++G(2d,p). Solvent effect was accounted for using the self-consistent reaction field (SCRF) method, with a SMD model and UAKS radii.16 Acetonitrile was used as the solvent. Solution-phase single-point energies corrected by the gas-phase Gibbs free energy corrections were used to describe all the reaction energy. All of these energies correspond to the reference state of 1 mol/L, 298 K. All energies reported throughout the text are in kcal/mol, and the bond lengths are in angstroms (Å). Structures were generated using GaussView 5.0.8 and CYL view.

Table S2. HOMO and LUMO energy levels of neutral CMP-1a,1b, and –SCN, as well as SOMO and SUMO levels of cationic CMP-1a-,1b- and •SCN, calculated by B3LYP/6-311+G**.

Compounds HOMO(eV) LUMO(eV)

O2 -3.59 CMP-1a -5.30 -3.19 CMP-1b -4.91 -2.74 -SCN -0.41 7.41 SOMO of of β-orbital (eV) SUMO of of α-orbital (eV) CMP-1a- -1.49 -0.65 CMP-1b- -2.10 -1.87 •_{SCN -8.23 -6.01}

Figure S28. Calculated energy diagrams in different photoreodx processes involving CMP-1a (a), 1b (b) and –SCN, according to Table S2.

Figure S29. (a) A Mott-Schottky curve of CMP-1, the flat band potential in n-type semiconductors is very close to that of conduction band (CB).4 (b) Schematic energy

band structure of CMP-1.

flat band potential: -0.98 V (equal to -1.82 eV)

VB (-3.32 eV) CB (-1.82 eV)

Figure S30. Temporal yield profiles for the reactions at two different concentrations of 6i ([6i]0 denotes the initial concentration of 6i). 6i was selected because of its

highest yield to give 8i. The black and red dot lines are fitted linearly from the experimental data. The slope of the black dot line (0.413 at [6i]0 = 0.1M) is twice that

of the red dot line (0.205 at [6i]0 = 0.05M), indicating first-order kinetics of the

photocatalytic reaction.5

Figure S31. Recycling performance of CMP-1.

Equ.S1 Equ.S2

Figure S32. Solid-state 13C NMR spectra of CMP-1 before (a) and after 5 photocatalytic cycles (b). The NMR spectra are basically identical, indicating no obvious chemical alteration of CMP-1 after catalytic utilization.

Figure S33. SEM image (a) and TEM image (b) of the recovered CMP-1 after the catalytic cycles.

5. 1H NMR and 13C NMR spectra of the thiocyanated anilines (8)

Figure S34. 1H NMR spectrum of 8a.

Figure S36. 1H NMR spectrum of 8b.

Figure S38. 1H NMR spectrum of 8c.

Figure S40. 1H NMR spectrum of 8d.

Figure S42. 1H NMR spectrum of 8e.

13

C NMR (CDCl3, 100 MHz)

Figure S44. 1H NMR spectrum of 8f.

Figure S46. 1H NMR spectrum of 8g.

Figure S48. 1H NMR spectrum of 8h.

Figure S50. 1H NMR spectrum of 8i.

Figure S52. 1H NMR spectrum of 8j.

Figure S54. 1H NMR spectrum of 8k.

Figure S56. H1-H1 COSY45 of 8k.

Figure S58. 1H NMR spectrum of 8l.

13

C NMR (CDCl3, 100 MHz)

Figure S60. 1H NMR spectrum of 8m.

Figure S62. 1H NMR spectrum of 8n.

Figure S64. 1H NMR spectrum of 8o.

Figure S66. 1H NMR spectrum of 8p.

Figure S68. 1H NMR spectrum of 8q.

Figure S70. 1H NMR spectrum of 8r.

Figure S72. 1H NMR spectrum of 8s.

Figure S74. 1H NMR spectrum of 8t.

Figure S76. 1H NMR spectrum of 8u.

Figure S78. 1H NMR spectrum of 8v.

Figure S80. 1H NMR spectrum of 8w.

Figure S82. 1H NMR spectrum of 8x.

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