Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst

A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880 m2/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity.

Powder X-ray diffraction (PXRD) patterns were recorded on a Rigaku XDS 2000 diffractometer using nickel-filtered Cu Kα radiation (λ = 1.5418 Å) over a range of 5° < 2θ < 40°. Simulations were made based on the single-crystal data using the Mercury software. The powder samples were mounted on clear cellophane tape and PXRD data were collected immediately after mounting.
The powder patterns were treated for amorphous background scatter. Thermogravimetric analysis (TGA) was performed on a Mettler Toledo TGA under air and nitrogen flows and heated from room temperature to 700 °C (at 10 °C/min).
Inductively coupled plasma optical emission spectroscopy (ICP-OES) was conducted on a Varian Vista MPX ICP-OES instrument that is equipped to cover the spectral range from 175 to 785 nm.
Samples for scanning electron microscopy (SEM) were sputtered with a layer of Os (5-nm thickness) prior to taking images on a Hitachi S-4800 SEM with a 15.0 kV accelerating voltage.
All adsorption and desorption measurements were performed on a Micromeritics Tristar 3020 (N2) system (Micromeretics, Norcross, GA) and measured at 77 K. Between 40-100 mg of samples were employed in each measurement and the data were analyzed using the ASAP 2020 instrument (Micromeretics, Norcross, GA). Before measurements, thermally activated samples were degassed for 12 h at 120 ºC under high vacuum (< 10-4 bar).
The pore size distributions were calculated from the adsorption-desorption isotherms. Sigma-Aldrich and used as received.

S3. Preparation of Fb-PPOP by thermal activation.
In a nitrogen glove box, a 20 mL microwave vial (capacity designates the amount of solution that can be safely loaded) equipped with a magnetic stir bar was charged with
The reaction mixture was heated at 170 °C for 24 h before being cooled to room temperature. The   Fe-PPOP S10

S12. Methanolysis of styrene oxide catalyzed by Fe-PPOP.
Styrene oxide (57 μL, 0.5 mmol), deuterated methanol (0.5 ml) and Fe-PPOP (10 mg, equivalent to 0.006 mmol Fe) were added to a 1 mL micro-centrifuge tube and then sealed. Then the vial was placed in a thermo-shaker at 55 °C for 24 h. NMR spectra were recorded at different time intervals.
Then at the end of the reaction, the vial was cooled to room temperature and opened. After catalyst separation by centrifugation, a small aliquot of the supernatant reaction mixture was taken to be analyzed by 1 [d] Selectivity (%) [d] TON/TOF(h -1 ) [ [b] Fe-PPOP 24 >99 100 82.5/3.43 5 [c] Fe(BTC) 24 72 [e] 95 [e] 59.7/2. Reaction between styrene oxide and MeOH without the catalyst at room-temperature gave no product in 12 h.
[b] Reusability of Fe-PPOP in the second run. S11 [c] Data derived from ref. [  [e] Determined by GC using nitrobenzene as the external standard.
[g] TON = turnover number (mmol of product per mmol of catalyst), TOF = turnover frequency (TON per time of reaction).  For the recycling experiment, the recovered catalyst was washed with acetonitrile and acetone, then centrifuged and the supernatant solution was decanted. This process was repeated for three times and then the dried catalyst was reused for the next cycle.  [b] Diastereselectivity (%) [c] TON/TOF (h -1 ) S14. ICP-OES Analysis.  This process was repeated for three times. The residue was then purified by chromatography on silica gel (n-hexane/ethyl acetate) to afford the pure product in 68% yield. The desired product was characterized by comparison of their physical and 1 H-NMR data with those of known compounds. 7 [d] Date derived from ref. [5] It should be noted that the reaction carried out in two steps and sequence addition.