Preparation and catalytic application of Mn(III)-porphyrin based micro sized porous coordination polymers

Transcription

1 Preparation and catalytic application of (III)-porphyrin based micro sized porous coordination polymers Sundol Kim a, Kyung Yeon Lee a, Young Sun Lee a, Ho Gyeom Jang a, Jung Kyoo Lee* b and Suk Joong Lee* a a Department of Chemistry, Research stitute for Natural Sciences, Korea University, 5 Anam-dong, Sungbuk-gu, Seoul , Korea b Department of Chemical Engineering, Dong-A University, Busan , Republic of Korea I. INTRDUCTIN NMR spectra were recorded on a Varian AS400 ( MHz for 1 H and MHz for 13 C) spectrometer. 1 H chemical shifts are referenced to the proton resonance resulting from protic residue in deuterated solvent and 13 C chemical shift recorded downfield in ppm relative to the carbon resonance of the deuterated solvents. Absorbance and emission spectra were obtained using an Agilent UV-Vis-NIR spectrophotometer using quartz cells. All scanning electron microscopy (SEM) images were obtained using a JELl JSM-7001F. Energy dispersive X-ray spectroscopy (EDX) was obtained using a Horiba EMAX Gatan at the Korea Basic Science stitute (KBSI) Seoul Center. Matrix- Assisted Laser-Desorption-Ionization Time-of-flight Mass Spectra (MALDI-TF) were obtained on a Bruker Daltonics LRF20 MALDI-TF Mass Spectrometer at the dustry-academic Cooperation Foundation, Yonsei University. Powder X-ray diffraction measurements were recorded with a Rigaku D/MAX Ultima III using nickel-filtered Cu K α radiation (λ = Å) over a range of 2 < 2θ < 40 and X celerator detector operating at 40 kv and 30 ma. Thermo Gravimetric Analyzer (TGA) measurements were carried out using a Scinco TGA N-1000 in a nitrogen atmosphere at a heating rate of 10 C/min in the temperature range of 25~900 C for particles. Gas chromatography was recorded using a Hewlett Packard HP 6890 series. Ultrapure grade ( %) N 2 gas was used for the gas sorption experiments. The N 2 adsorption/desorption analysis was performed on a Belsorp-miniII at 77 K (BEL Japan). The samples were dried at room temperature for 2 h under high vacuum before measurements. II. MATERIALS {5,15-bis(4-carboxyphenyl)-10,20-bis[2,6-diethoxyphenyl]porphyrinato} manganese(iii) chloride, {5,15-bis(4- carboxyethylphenyl)-10,20-bis[2,6-diethoxyphenyl] porphyrinato}manganese(iii) chloride and 2-(tertbutylsulfonyl)iodosylbenzene were synthesized by according to previously reported procedures [1]. All other chemicals were obtained from commercial sources and used without further purification. All of the reactions and manipulations of the porphyrin building blocks were carried out under N 2 with the use of standard inert-atmosphere and Schlenk techniques unless otherwise noted. Solvent used in inert-atmosphere reactions were dried and degassed using standard procedures. Flash column chromatography was carried out with mesh silica gel from Merck using wet-packing method. All deuterated solvents were purchased from Cambridge Isotope Laboratory.

2 Scheme S1. Synthesis of (III)-porphyrins III. PWDER XRD PATTERNS (PXRD) d c b θ (degree) a Fig. S1. The PXRD patterns of mpcps obtained with addition of various amount of water; a) micro-rose (mpcp-1), b) elongated bipyramid (mpcp-2), c) micro-bellow (mpcp-3) and d) micro-bowtie (mpcp-4)

3 IV. EDX ANALYSIS C C a b C C c d Fig. S2. EDX data of mpcps obtained with addition of various amount of water; a) micro-rose (mpcp-1), b) elongated bipyramid (mpcp-2), c) micro-bellow (mpcp-3) and d) micro-bowtie (mpcp-4). sets: SEM images of mpcps taken during the EDX analysis V. TEHERMGRAVIMETRIC ANALYSIS (TGA) Weight (%) Weight (%) Temperature ( o C) - MeH H 2 DMF (~7 wt%) Temperature ( o C) a b c d Fig. S3. Thermogravimetric analysis (TGA) of mpcps obtained with addition of various amount of water; a) micro-rose (mpcp-1), b) elongated bipyramid (mpcp-2), c) micro-bellow (mpcp-3) and d) micro-bowtie (mpcp-4). set shows clearly the loss of solvent

4 VI. GAS SRPTIN ANALYSIS Ultrapure grade (99.999%) N2 was used for the gas sorption experiments. The N2 sorption analysis was performed on a Belsorp-miniII at 77 K (BEL Japan). The samples were dried at 375 K under high vacuum for 2 h before measurements. The equipment was calibrated by using Cu-BTC (HKUST-1) as a reference material [2]. Table S1. Surface area measurements of PCP particles Sample BET (m2/g) Vp (cm3/g) mpcp mpcp mpcp mpcp Fig. S4. SEM image of mpcp-2 activated for the gas adsorption experiment

5 VII. CATALYSIS Table S2. vestigation of the recyclability a cat. xidant cb Number of catalytic cycles Conversion, % 80.7 c a Reaction conditions; styrene: 35 µmol, oxidant: 50 µmol, mpcp-2 (catalyst): 4.5 µmol, CH 2 Cl 2 : 1 ml, reaction time: 30 min, rt. b xidant: 2-(tert-butylsulfonyl)iodosylbenzene. c Conversion (%) determined by GC with dodecane as an internal standard. Conversion (%) Cyclopentene 1-Hexene Styrene (Z)-Stilbene (E)-Stilbene Time (min) Fig. S5. Time conversion plot for the oxidation of selected substrates with mpcp-2. Reaction condition; olefin: 70 µmol, oxidant (2- (tert-butylsulfonyl)iodosylbenzene): 100 µmol, catalyst 9.2 µmol, CH 2 Cl 2 : 2 ml, room temperature). The conversions of substrates were determined by GC with dodecane as an internal standard Before After Fig. S6. SEM images of recovered mpcp-2 after the oxidation (right)

6 VIII. REFERENCES 1. (a) Lee DH, Kim S, Hyun MY, Hong J-Y, Huh S, Kim C and Lee SJ. Chem. Comm. 2012; 48: 5512; (b) Schmidt I, Jiao J, Thamyongkit P, Sharada DS, Bocian DF and Lindsey JS. J. rg. Chem. 2006; 71: 3033; (c) Geier III GR, Ciringh Y, Li F, Haynes DM and Lindsey JS. rg. Lett. 2000; 2: 1745; (d) Macikenas D, Skrzypczak-Jankun E and Protasiewicz JD. J. Am. Chem. Soc. 1999; 121: Regan B, Grätzel M. nature 1991; 353: Chui SS-Y, Lo SM-F, Charmant JPH, Guy rpen A and Williams ID. Science 1999; 283: 1148.