Supporting Information forTethering of Cu(II), Co(II) and Fe(III) tetrahydro-salen and salen complexes onto amino-functionalized SBA-15: Effects of salen ligand hydrogenation on catalytic performances for aerobic epoxidation of styreneYing Yanga, Ying Zhangb, Shijie Haob, Qiubin Kanaa College of Chemistry, Jilin University, Changchun 130023, Jilin, PR Chinab Department of Materials Science and Engineering, China University of Petroleum, Changping District, Beijing, 102249, PR ChinaSynthetic procedures:1. Preparation of pure siliceous SBA-15Typically, 2.0 g triblock copolymer (P123) was dissolved in 60 ml of 2.0 mol/l HCl and 15 ml of distilled water at 40 oC, and then the mixture was stirred for 1 h. After that, 4.17 ml of tetraethoxysilane (TEOS) was added. The gel composition P123: HCl: H2O: TEOS was 0.017: 5.88: 197: 1 in molar ratio. The resulting mixture was further stirred at 40 oC for 5 h, and then transferred into a teflon-lined stainless steel autoclave and aged at 100 oC for 24 h. After cooling down to room temperature, the products were filtered, washed with distilled water repeatedly, and dried overnight at 60 oC in air. The as-synthesized sample was calcined at 550 oC (heating rate 1 oC/min) for 16 h to remove the copolymer template.2. Preparation of amino-functionalized SBA-151.0 g of calcined SBA-15 (pre-dried at 120 oC for 2 h) was added to 100 ml of dry toluene in a 250 ml flask, and the flask was flushed with nitrogen for 20 min. Then 0.54 ml of 3-aminopropyltriethoxysilane (APTES) was added and stirred for 24 h. Then the solid was filtrated, washed with toluene and ethanol, and dried in air. And the received solid was denoted as APS-SBA-15. Found for APS-SBA-15: C, 5.37; H, 1.41; N, 1.39%. FTIR (KBr pellets, cm-1): 1510 (NH2), 1130-1000 (Si-O-Si), 960 (Si-OH), 687 (N-H). 3. Synthesis of 5-chloromethylsalicylaldehyde (5-CM-Sal)5-chloromethylsalicylaldehyde was synthesized from salicylaldehyde by the classical chloromethylation method. In a typical synthesis, 17.5 g (160 mmol) of salicylaldehyde was treated with 24 ml of 38% aqueous formaldehyde and 1.2 g of ZnCl2 in 100 ml of con. HCl. The mixture was stirred at room temperature under N2 atmosphere for 24 h. The resulting white solid was filtered and repeatedly extracted with diethyl ether. The combined organic phases were washed with saturated aqueous NaHCO3 and water and then dried over MgSO4. The viscous oil was obtained by distillation and then subjected to crystallization in petroleum ether. The extract furnished 5-chloromethylsalicylaldehyde as white-colored needles (9.0 g, 32.0% yield). Found: C, 57.57; H, 4.12%. Calc. for C8H7O2Cl: C, 56.30; H, 4.10%. FTIR (KBr pellets, cm-1): 3240 (OH), 2925, 2873, (Aliph-H), 1659 (C=O), 1260 (CH2Cl), 772 (C-Cl) (Fig. S1). UV-vis, (nm): 224, 257, 332. 1H NMR (CDCl3, TMS, ppm): 11.07 (1H, s, OH), 9.90 (1H, s, CHO), 7.59 (1H, s, Ar-H), 7.26-7.19 (1H, d, Ar-H), 7.02-6.08 (1H, d, Ar-H), 4.59 (1H, s, CH2Cl) (Fig. S2).4. Synthesis of N,N-bis(5-chloromethylsalicylidene)ethylenediamine (CM-SalenH2) 3.41 g (20.0 mmol) of 5-chloromethylsalicylaldehyde was dissolved in 10 ml of CH2Cl2. A solution of ethylene diamine (0.67 ml, 10 mmol) in 10 ml of CH2Cl2 was then added. The resulting solution was stirred at room temperature for 24 h. After the solvent was removed under vacuum, the product was obtained as bright yellow crystals. Found: C, 58.50; H, 5.10; N, 7.86%. Cal. for C18H18N2O2Cl2: C, 59.20; H, 4.90; N, 7.70%. FTIR (KBr pellets, cm-1): 3423 (OH), 2929, 2887 (Aliph-H), 1647 (C=N), 1262 (CH2Cl), 769 (C-Cl). UV-vis, (nm): 252, 340, 381. 1H NMR (DMSO-d6, TMS, ppm): 11.12 (2H, s, OH), 7.83-6.98 (6H, m, Ar-H), 8.40, 8.44 (2H, s, CH=N), 4.44 (4H, s, CH2Cl), 3.48-3.38, 3.19-3.10 (4H, t, N-CH2-CH2-N) (Fig. S3).5. Preparation of SalenH2 and H4SalenH2SalenH2 ligands were prepared as follows: 0.1 mol of ethylenediamine was dissolved in 25 ml ethanol. The obtained solution was then slowly added to a solution composed of 0.2 mol salicyladehyde and 150 ml ethanol under stirring conditions. The resultant solution was further refluxed for 1 h, resulting in the precipitation of a yellow solid, which was filtered and recrystallized from ethanol. 1H NMR (CDCl3) of SalenH2: 13.20 (2H, s, OH), 8.35 (2H, s, CH=N), 7.30-6.82 (8H, m, Ar-H), 3.91 (4H, s, N-CH2CH2-N) (Fig. S4a). FTIR (KBr pellets, cm-1): 3420 (OH), 3054 (C=C), 2925, 2893 (Aliph-H), 2731-2585 (hydrogen bonding), 1635 (C=N), 1600, 1496, 1453 (Ph). UV-vis, (nm): 265, 349, 370, 425.H4SalenH2 was prepared as follows: 0.01 mol SalenH2 was dissolved in 60 ml methanol, followed by the addition of 0.011 mol of NaBH4 at ambient temperature. After stirring for 2 h, the solvent was removed by distilling under vacuum conditions. The solid product was further washed with distilled water and recrystallized from ethanol. The 1H NMR (CDCl3) of H4SalenH2: 7.25-6.78 (8H, m, Ar-H), 3.99 (4H, s, N-CH2CH2-N), 2.84 (4H, s, N-CH2)