Microporous, Tetraarylethylene-based Polymer Networks generated in a Reductive Polyolefination Process

MPNs that contain aggregate-induced emission (AIE)-active tetraphenylethylene (TPE) or other tetraarylethylene units have been generated in a reductive polyolefination process starting from four different tris( , -dichlorobenzyl)arene derivatives with dicobalt octacarbonyl or chromium(II) acetate as reductive olefination agents. Microporosity with moderately high BET surface areas up to 500 m2/g could be combined with high solid state photoluminescence quantum yields up to 25.3 %. Microporous, Tetraarylethylene-based Polymer Networks generated in a Reductive Polyolefination Process

Solid-State NMR measurements.Solid-state 13 C CPMAS spectra were collected at 75.48 MHz using a Bruker Avance III 300 spectrometer with a contact time of 2.5 ms coadding 4096 up to 16392 transients, depending on the required relaxation delay of 2 s up to 60 s.All experiments were carried out at room temperature using a standard Bruker 4 mm double resonance MAS probe spinning at 12 kHz, typical π/2-pulse lengths of 4 µs and SPINAL64 proton decoupling.The spectra were referenced with respect to tetramethyl silane (TMS) using solid adamantane as secondary standard (29.46 ppm for 13 C).
UV-Vis.UV-Vis absorption spectra were recorded on a Shimadzu UV-2401 PC spectrophotometer at room temperature.
Photoluminescence spectroscopy.Fluorescence measurements were carried out on Fluoromax-4 equipped with Quanta-Phi integration sphere (Horiba) by using a powder sample holder at room temperature.

Gas adsorption selectivities.
To evaluate the gas adsorption selectivity CO 2 /CH 4 and N 2 /H 2 Henry´s law was used: q = K * P where q is the adsorbed amount per unit weight of adsorbent (cm 3 g -1 ), P is the adsorbate gas pressure at equilibrium (torr), and K is the Henry´s law constant (cm 3 g -1 torr -1 ) and the related selectivities are calculated with the equation S ij = K (i) / K (j) [3].

Supercritical carbon dioxide treatment (washing).
Prior to the supercritical drying process all samples were soaked with absolute ethanol (72 h).The drying procedure was performed in a supercritical point dryer from TousimisTM (Samdri -795) with liquid CO 2 (Messer) as carbon dioxide source.The dry samples were obtained after four drying cycles: The ethanol-containing samples were placed inside the dryer and the ethanol was exchanged by rinsing with liquid CO 2 (l) over a period of 15 min.After that the chamber was sealed and the temperature was raised to 40 °C resulting in a chamber pressure of around 1300 psi well above the critical point of CO 2 .The chamber was held above the critical point for 1 h.This procedure was repeated for additional three times with the following modifications: second run: 5 min purging, 1 h supercritical conditions, third run: 5 min purging, 2.5 h supercritical conditions; last run 5 min purging, 14 h supercritical conditions.

PL quenching experiments.
For preparation of polymer pellets 50 mg of P4 was compressed (3 tons) for 20 min.The vapor chamber was saturated with the analyte for 24 h prior to the PL quenching experiments.
The reaction mixture was refluxed for 24 h.A large amount of cold water was added to quench the reaction and the reaction mixture was then extracted with DCM.The organic layer was washed with water and dried over magnesium sulfate.After filtration and solvent evaporation, the crude product was purified by silica-gel column chromatography with hexane/DCM (2:3 by volume) as eluent.The product was obtained as a white solid (38.6 g, 94 %).4-Bromoacetophenone (3.5 g, 17.42 mmol) was dissolved in ethanol (55 mL) at 0 °C.
Tetrachlorosilane (22.2 g, 131 mmol) was added slowly to the reaction mixture at 0 °C and stirred over night at ambient condition.The reaction mixture was poured into an ice/water mixture and was extracted with DCM.The crude product was purified by silica-gel column chromatography in a hexane/DCM gradient from 2 to 50 % of DCM, followed by a recrystallization from a mixture of ethanol and chloroform.The product was obtained as a white solid (2.0 g, 63 %).hydrochloride solution the reaction mixture was refluxed for an addition 1 h.The resulting mixture was extracted three times with diethylether and dried over magnesium sulfate.

Tris(2,4,6-benzoyl)-1,3,5-triazine M3
Carefully dried potassium 1,3,5-triazine-2,4,6-tricarboxylate [6][7][8] (5.0 g, 15.27 mmol) was suspended in POCl 3 (50 mL, freshly distilled) and the mixture was stirred for 12 h at room temperature and for additional 12 h at 80°C.The color of the suspension gradually turned to yellow-brownish and a solid residue is formed.Excess of POCl 3 is distilled off under reduced pressure.The solid residue was suspended with dry benzene (80 mL) and aluminum chloride (7.3 g, 55.00 mmol) was added under external cooling with ice.The dark red suspension was stirred for 4 h at room temperature and then poured into a mixture of 100 g of ice and 100 mL of concentrated hydrochloric acid.Next, the organic products were extracted with toluene.
After drying the organic phase over calcium chloride the solvent was removed under reduced pressure.The product was recrystallized from toluene to yield (3.5 g, 58 %) of white needles. .
BET: 200 m 2 /g, total pore volume: 1.05 cc/g.4-Methylbenzonitrile (29.4 g, 251 mmol) was added to trifluoromethane sulfonic acid (30 mL, 338 mmol) at 0 °C under inert atmosphere.The mixture solidifies and after 3 d at room temperature the mixture was heated up to 65 °C for additional 4 h.The product was purged into 2 L of an ice/water mixture and extracted three times with diethylether.The organic phase was dried over magnesium sulfate and concentrated under reduced pressure.The crude solid product was recrystallized from toluene (24.0 g, 82 %) white crystals.Recrystallization of the crude product from N,N-dimethylformamide yielded (5.2 g, 83 %) a white powder.were added and the mixture was refluxed for 2 h till a clear solution is formed.Excess of thionyl chloride and benzene were removed under reduced pressure.The solid residue was redissolved in benzene (100 mL).This solution and aluminum chloride (6.0 g, 45.3 mmol) were added to a 250 mL one-necked round-bottom flask.The reaction mixture was stirred at room temperature for 24 h.The mixture was purged into cold water and then extracted with DCM.
The organic phase was isolated, washed with water and finally dried over magnesium sulfate.
After removing the solvent the crude product was purified by silica-gel column chromatography with hexane/DCM (2:3 by volume) as eluent.The product was obtained as white solid (1.5 g, 23 %).(2.0 g, 9.65 mmol) and 20 mL of chlorobenzene were placed into to a 100 mL Schlenk tube.
The reaction mixture was stirred at 120 °C for 4 d.The resulting mixture was cooled to 80 °C.
Chlorobenzene and POCl 3 were destilled off under reduced pressure.Finally, unreacted phosphorus pentachloride was sublimed out of the reaction mixture under reduced pressure.
The resulting yellow oil (1.26 g, 99 %) was used without further purification.83 mmol) and 20 mL chlorobenzene were added to a 100 mL Schlenk tube.The mixture was reacted at 100 °C for 50 min (gas formation starts at around 80 °C).
For quenching, 10 mL of 1,2-dibromoethane was added and the mixture was stirred for another 10 min.Next, the reaction mixture was purged into methanol, the solid product collected by filtration and washed with methanol.The crude product was purified by successive Soxhlet extraction with methanol, ethyl acetate, 1,4-dioxane and chloroform.The resulting polymer was treated (washed) with supercritical carbon dioxide.The product was obtained as a yellow powder (960 mg, quantitative yield).PL: λ max (solid state)/nm: 560 nm (excitation 400 nm); PLQY: 25.3 %.

Polymer network P1 (Co 2 (CO) 8 as condensing agent) 1
,3,5-Tris(α,α-dichlorobenzyl)benzene MCl1 (1.3 g, 2.27 mmol), dicobalt octacarbonyl (2.7 g, 7.83 mmol) and 20 mL of chlorobenzene were added to a 100 mL Schlenk tube.The reaction mixture was heated at 100 °C for 50 min (gas formation starts at around 80 °C).For quenching, 10 mL of 1,2-dibromoethane was added and the mixture was stirred for another 10 min.Next, the reaction mixture was purged into methanol and the solid powder collected by filtration and washed with methanol.The crude product was purified by successive Soxhlet extraction with methanol, ethyl acetate, 1,4-dioxane, and chloroform.The resulting polymer was treated (washed) with supercritical carbon dioxide.The product was obtained as a yellow powder (828 mg, quantitative yield).