Supporting Information

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1 Supporting Information A Sn IV -Porphyrin-Based Metal-Organic Framework for the Selective Photo-Oxygenation of Phenol and Sulfides Ming-Hua Xie, Xiu-Li Yang, Chao Zou and Chuan-De Wu* Department of Chemistry, Zhejiang University, Hangzhou, , P. R. China cdwu@zju.edu.cn Materials and General Procedures All of the chemicals were obtained from commercial sources and were used without further purification, except Sn(IV)(OH) 2 TPyP was synthesized according to the literature method. 1 IR spectrum was recorded from KBr pellet on a FTS-40 spectrophotometer. Elementary analysis was performed on a ThermoFinnigan Flash EA 1112 element analyzer. Powder X-ray diffraction data (PXRD) was recorded on a RIGAKU D/MAX 2550/PC for Cu-Kα (λ = Å). Thermogravimetric analysis (TGA) was carried out on an SDT Q600 compositional analysis instrument from 30 to 1000 C under N 2 atmosphere at a heating rate of 10 C/min. GC-MS were recorded on a SHIMADZU GCMS-QP2010. Photo-oxygenation reactions were carried out using fiber optics of a 350 W Xe lamp or 300 W Hg lamp source. The determination of the unit cell and data collections for the crystal of 1 were performed on a CrysAlisPro program. The data were collected using graphite monochromatic Mo-Kα radiation (λ = Å) at 293 K. The data sets were corrected by empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. 2 The structure was solved by direct methods, and refined by full-matrix least-square methods with the SHELX-97 program package. 3 The solvent molecules and nitrate anions in compound 1 are highly disordered, and attempts to locate and refine the peaks were not successful. SQUEEZE subroutine of the PLATON software suit was used to remove the scattering from the highly disordered guest molecules and nitrate anions. 4 The resulting new file was used to further refine the structure. Synthesis of [Zn 2 (H 2 O) 4 Sn IV (TPyP)(HCOO) 2 ] 4NO 3 DMF 4H 2 O (1): Sn IV (OH) 2 TPyP (10 mg, mmol) was thoroughly dissolved in 3 ml CH 2 Cl 2, which was dropwise added into a 10 ml DMF solution of Zn(NO 3 ). 2 6H 2 O (50 mg, mmol) under stirring at room temperature. S1

2 Subsequently, ml of HCl (0.8 M) was added into the mixture under stirring. The resulting purple solution was heated at 50 o C for 5 days. Dark purple crystals of 1 were isolated by filtration, washed with MeOH and Et 2 O, and dried in air. Yield: 8.1 mg (43.8% based on Sn IV (OH) 2 TPyP). Anal. Calcd. for 1 (%): H, 3.47; C, 38.03; N, Found: H, 3.56; C, 38.16; N, IR (KBr pellet, ν/cm -1 ): 1613s, 1491w, 1420m, 1384m, 1214w, 1085w, 1071w, 1025m, 858w, 805m, 684w. A typical procedure for the photo-oxygenation of 1,5-dihydroxynaphthalene: Solid 1 (0.005 mmol) and 1,5-dihydroxynaphthalene (0.05 mmol) in a mixed solvent of CH 2 Cl 2 /MeOH (4 ml / 1 ml) were stirred at room temperature under the irradiation of a 350 W Xe lamp for 3.5 h in the presence of O 2. The filtrate was evaporated under reduced pressure at room temperature. The identity and yield of the product were determined by GC-MS. A typical procedure for the reuse of Sn IV (OH) 2 TPyP in the catalytic photo-oxygenation of 1,5-dihydroxynaphthalene: Sn IV (OH) 2 TPyP (0.01 mmol) and 1,5-dihydroxynaphthalene (0.1 mmol) were dissolved in a mixed solvent of CH 2 Cl 2 /MeOH ( 4mL/1 ml). The resulting mixture was stirred at room temperature under the irradiation of a 350 W Xe lamp for 3.5 h in O 2 atmosphere, which was subsequently evaporated under vacuum. The resulting solid was washed with ethyl ether for three times. The combined Et 2 O solution was subjected to GC-MS analysis, while the recovered Sn IV (OH) 2 TPyP solid was subsequently used in the successive run. A typical procedure for the photo-oxygenation of sulfides catalyzed by 1: Sulfide (0.05 mmol) and solid 1 (0.005 mmol) in a mixed solvent of CH 2 Cl 2 /MeOH (4 ml / 1 ml) were stirred at room temperature under the irradiation of a 350 W Xe lamp for 12 h in the presence of O 2. The filtrate was evaporated under reduced pressure at room temperature. The identity and yield of the product were determined by GC-MS. References 1. Langford, S. J.; Woodward, C. P. CrystEngComm 2007, 9, CrysAlisPro, version ; Oxford Diffraction Ltd.: Oxfordshire, U.K., Sheldrick, G. M. Program for Structure Refinement: University of Göttingen, Germany, Spek, A. L. J. Appl. Crystallogr., 2003, 36, 7. S2

3 Figures: Figure S1. FT-IR spectrum of Weight / % Temperature / o C Figure S2. TG result of 1 S3

4 Figure S3. Powder X-ray diffraction patterns for compound 1. Figure S4. GC trace for 1,5-dihydroxynaphthalene. S4

5 Figure S5. GC trace of the catalytic result for the selective photo-oxygenation of 1,5-dihydroxynaphthalene catalyzed by solid 1. Figure S6. MS spectrum for the product at min. Figure S7. GC trace for methyl(phenyl) thioether. S5

6 Figure S8. GC trace of the catalytic result for the selective photo-oxygenation of methyl(phenyl) thioether catalyzed by solid 1. Figure S9. MS spectrum for the product at min. S6

7 Tables: Table S1. Crystal data and structure refinements for 1. Compound 1 Formula C 45 H 49 N 13 O 25 SnZn 2 Formula weight Crystal color Dark purple Crystal system Tetragonal Space group P4/mbm a (Å) (3) c (Å) (5) Volume (Å 3 ) (3) Z 2 Calculated density (g cm -3 ) F(000) 1440 Temperature (K) 293(2) Wavelength (Å) Absorption coefficient (mm -1 ) θ for data collection ( o ) 3.56 to Limiting indices -25 h 22, -24 k 25, -10 l 9 Reflections collected [R(int) = ] Data / parameters 1959 / 128 Goodness-of-fit on F R1 (wr2) [I > 2σ(I)] (0.2271) R1 (wr2) (all data) (0.2416) R1 = ( F o F c ) / F o, wr2 = [ w(f 2 o F 2 c ) 2 / w(f 2 o ) 2 ] 0.5. S7

8 Table S2. Catalytic photo-oxygenation of 1,5-dihydroxynaphthalene. OH OH O hv Cat. OH O Entry Cat. Light Loading% Time(h) Oxidant Solvent Yield% Source 1 1 Xe(350W) Air CH 2 Cl 2 /MeOH(4:1) 40 a 2 1 Xe(350W) O 2 MeOH Xe(350W) O 2 CH 2 Cl Xe(350W) O 2 CH 3 CN Xe(350W) O 2 H 2 O Xe(350W) O 2 THF Hg(300W) O 2 CH 2 Cl 2 /MeOH(4:1) > Sn IV (OH)2TPyP Hg(300W) O 2 CH 2 Cl 2 /MeOH(4:1) > Sn IV (OH)2TPyP Hg(300W) O 2 CH 2 Cl 2 /MeOH(4:1) 14 b 10 Sn IV (OH)2TPyP Hg(300W) O 2 CH 2 Cl 2 /MeOH(4:1) 7 c 11 1 Dark O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) 10 1 O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) 10 2 O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) 10 3 O 2 CH 2 Cl 2 /MeOH(4:1) 98 a For 60 h. b The second run. c The third run. S8

9 Table S3. Catalytic photo-oxygenation of sulfides. O O R 1 Cat. S O S S R 2 2 R 1 R R hv 1 2 O R 2 Entry Cat. Light Loading% Time(h) Oxidant Solvent Conv.% Selectivity Source Sulfoxide Sulphone 1 1 Xe(350W) Air CH 2 Cl 2 /MeOH(4:1) 71 > Xe(350W) O 2 MeOH > Xe(350W) O 2 CH 2 Cl Xe(350W) O 2 CH 3 CN Xe(350W) O 2 H 2 O Xe(350W) O 2 THF Hg(300W) O 2 CH 2 Cl 2 /MeOH(4:1) > Dark O 2 CH 2 Cl 2 /MeOH(4:1) Xe(350W) 8 12 O 2 CH 2 Cl 2 /MeOH(4:1) 94 > Xe(350W) 4 12 O 2 CH 2 Cl 2 /MeOH(4:1) 84 > Xe(350W) 1 12 O 2 CH 2 Cl 2 /MeOH(4:1) 35 > Xe(350W) 0 12 O 2 CH 2 Cl 2 /MeOH(4:1) 5 > Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) 10 > Xe(350W) 10 1 O 2 CH 2 Cl 2 /MeOH(4:1) 15 > Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) 22 > Xe(350W) 10 2 O 2 CH 2 Cl 2 /MeOH(4:1) 34 > Xe(350W) O 2 CH2Cl2/MeOH(4:1) 46 > Xe(350W) 10 3 O 2 CH 2 Cl 2 /MeOH(4:1) 61 > Xe(350W) 10 4 O 2 CH 2 Cl 2 /MeOH(4:1) 72 > Xe(350W) 10 5 O 2 CH 2 Cl 2 /MeOH(4:1) 83 > Xe(350W) 10 6 O 2 CH 2 Cl 2 /MeOH(4:1) 91 > Xe(350W) 10 7 O 2 CH 2 Cl 2 /MeOH(4:1) 95 > Xe(350W) 10 8 O 2 CH 2 Cl 2 /MeOH(4:1) 98 > Xe(350W) 10 9 O 2 CH 2 Cl 2 /MeOH(4:1) 99 > Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) 99.5 > Xe(350W) O 2 CH 2 Cl 2 /MeOH(4:1) 99.8 > S9