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Supporting Information

Rhodium Hydrogenation Catalysts Supported in Metal Organic Frameworks: Influence of the Framework on Catalytic Activity and Selectivity

Douglas T. Genna, Laura Y. Pfund, Danielle C. Samblanet, Antek G. Wong-Foy, Adam

J. Matzger, and Melanie S. Sanford*

Department of Chemistry, University of Michigan, 930 N. University Avenue, Ann Arbor, MI 48109

Corresponding Author * mssanfor@umich.edu Table of Contents:

I. Materials and Methods...……………………………………………….……....S2

II. Synthesis of MOFs……………………………………….…..………………….S4

III. Catalytic Hydrogenation Procedures…………...…………………………...S6

IV. Supplemental Figures……………………………………..…………….........S13

V. References……………………………………………………………………….S21

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I. Materials and Methods All high-pressure reactions were carried out using a Parr Model 5000 Multiple Reactor system that includes six 50 mL stainless steel vessels equipped with flat gaskets and head mounting valves. The system is operated with a 4871 process controller and SpecView version 2.5 software. ICP-OES data was obtained on a Perkin-Elmer Optima 2000 DV with Winlab software. Powder X-ray diffraction (PXRD) patterns were collected at room temperature using a Rigaku R-Axis Spider diffractometer with an image plate detector and graphite monochromated Cu-Kα radiation (λ = 1.54187 Å). Samples were mounted on a CryoLoop, and images were collected for three minutes while rotating the sample about the φ-axis at 10°/s, oscillating ω between 120° and 180° at 1°/s with χ fixed at 45°. Images were integrated from 2 to 70° with a 0.01° step size using AreaMax 2.0 software (Rigaku). Powder patterns were processed using Jade 8 XRD Pattern Processing, Identification & Quantification analysis software (Materials Data, Inc). Analysis of Merrifield resin was performed by Raman spectroscopy with a Renishaw inVia Raman Microscope equipped with a 785 nm diode laser and a RenCam CCD detector. The 785 nm diode laser has a grating with 1200 lines/mm and a 65 µm slit. Spectra were collected and analyzed using the WiRE 3.4 software package (Renishaw). Calibration was performed using a silicon standard. Spectra were collected using an Olympus SLMPlan 20× objective (numerical aperture = 0.35) in extended scan mode with a range of 100-3800 cm-1. Spectra were further analyzed using ACD/SpecManager Version 12.01 software 3 (ACD/Labs). Centrifugation was performed on a Sorval ST 16 centrifuge from ThermoScientific. High pressure Raman data were collected using a Renishaw inVia Raman Microscope equipped with an Innovative Photonics Solutions 785 nm spectrum stabilized laser module and a RenCam CCD detector. The 785 nm spectrum stabilized laser module has a grating with 1200 lines/mm and a 65 µm slit. In situ Raman analysis was performed with an Inphotonics RamanProbe Fiber Optic Sampling Probe with a 50 µm excitation core fiber with an FC connector and a 100 µm collection core fiber also with an FC connector. The high pressure experiments were performed in a 45 mL Parr cylinder with a 3/8 inch NPT in the bottom. The probe was swaged into a 3/8 inch Swagelok straight fitting male connector, which was then fitted into the bottom of the reactor via the 3/8 inch NPT. Spectra were collected via the RamanProbe in extended scan mode with a range of 300-3200 cm-1. They were analyzed using the WiRE 3.4 software package’s curve fitting analysis for peaks at 1643 cm-1 for the double bond in 1-octene, 1657 cm-1 for the double bond in trans-2-octene, and 1660 cm-1 for the double bond in cis-2-octene. Calibration was performed using a toluene standard. NMR spectra were obtained on a Varian VNMRS 500 (500.10 MHz for 1H). Gas chromatography was carried out on a Shimadzu 17A GC using a Restek Rtx®-5 (Crossbond 5% diphenyl – 95% dimethyl polysiloxane; 15 m, 0.25 mm ID, 0.25 µm df) column.

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1-Octene, 1,2-bis(diphenylphosphino)ethane, and InCl3 were purchased from Acros Organics. Acetone (reagent grade), DMF (anhydrous), dioxane, 5-hexen-1-ol, Merrifield resin (70-90 mesh, 1.88 mmol/g), and [Rh(CH3CN)2(COD)]BF4, were purchased from Sigma-Aldrich. The [Rh(CH3CN)2(COD)]BF4 was stored and weighed in the glovebox. 2,3-Dimethylbutene and monosodium 2-sulfoterephthalic acid were purchased from TCI America. C6D6 was purchased from Cambridge Isotope Laboratories. Ultra high purity H2 was purchased from Purity Cylinder Gas Inc. Ricca Chemical brand 1000 ppm ICP standards were purchased from Fisher Scientific. Nitric acid and hydrochloric acid were purchased from EMD Millipore. All chemicals were used as received. 1,3,5-Tris(4-carboxyphenyl)benzene (H3BTB) was synthesized as reported in the literature.1 ZJU-28, and ZJU-28-1a were synthesized as reported in the literature.2 Octa-t-butyl-octa-O-allylcalix[8]arene and tetra-t-butyl-tetra-O-allylcalix[4]arene were synthesized as reported in the literature.3,4

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II. Synthesis of MIL-101-SO3 and MIL-101-1a–f

Synthesis of MIL-101-SO35

Concentrated hydrochloric acid (0.75 mL, 25.0 mmol) was added to 100 mL Erlenmeyer flask charged with deionized water (50 mL). Monosodium 2-sulfoterephthalic acid (3.35 g, 12.5 mmol) and CrO3 (1.25 g, 12.5 mmol) were then added sequentially. The resulting solution was transferred in three equal portions into 20 mL Teflon-lined stainless steel autoclaves. The sealed autoclaves were each heated at 180 ºC in an oven for 6 d. The autoclaves were then slowly cooled to room temperature. The resulting green solids were combined and washed with deionized water (3 x 35 mL) and methanol (3 x 25 mL). The solids were then dried at room temperature under high vacuum for 20 h. The average yield was 35%.

Synthesis of MIL-101-SO3-1a

[Rh(CH3CN)2(COD)]BF4 (28 mg, 0.074 mmol) and DMF (2 mL) were combined in a 4 mL scintillation vial (with no precaution to exclude air) followed by the addition 1,2-bis(diphenylphosphino)ethane (29 mg, 0.074 mmol). The resulting solution was allowed to stand for 30 min. At this time, the solution was added to a suspension of MIL-101-SO3 (100 mg) in DMF (3 mL) in a separate 20 mL scintillation vial. The vial was capped and placed in an orbital shaker for 3 d. The mother liquor was then decanted away from the crystals, and the crystals were washed with fresh DMF until the washings were colorless (~4 x 10 mL DMF). The metal-impregnated MOF was then dried at room temperature under high vacuum for 20 h. The material was analyzed by ICP-OES for Rh content and by PXRD for crystallinity (Figure S1).

Synthesis of MIL-101-SO3-1b

MIL-101-SO3 (100 mg) was suspended in DMF (3 mL) in a 20 mL scintillation vial. A solution of 1b (0.074 mmol) in DMF (2 mL) was added to the MOF suspension. The vial was capped and placed in an orbital shaker for 3 d. The mother liquor was then decanted away from the crystals, and the crystals were washed with fresh DMF until the washings were colorless (~4 x 10 mL DMF). The metal-impregnated MOF was then dried at room temperature under high vacuum for 20 h. The material was analyzed by ICP-OES for Rh content and by PXRD for crystallinity (Figure S1).

Determination of wt % metal uptake by MIL-101-SO3.

1-2 mg of MOF were digested in nitric acid (2 mL) and diluted with H2O such that the final volume was 10 mL. This solution was subjected to ICP-OES analysis and the wt % uptake of Rh was determined by comparison to the wt % chromium (Cr) using the following equation:

𝑤𝑡%  𝑅ℎ = (𝑤𝑡%  𝐶𝑟)  𝑝𝑝𝑚  𝑅ℎ𝑝𝑝𝑚  𝐶𝑟

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where wt% Cr = 9.5%, as determined from the molecular formula of MIL-101-SO3.5

Synthesis of ZJU-282,6

1,3,5-Tris(4-carboxyphenyl)benzene (H3BTB) (532 mg, 1.20 mmol, 1.00 equiv) and InCl3 (582 mg, 2.40 mmol, 2.00 equiv) were dissolved in a pre-mixed solution of DMF (36 mL), 1,4-dioxane (24 mL), deionized H2O (4 mL), and HNO3 (0.25 mL). The resulting cloudy solution was filtered through a Fisher-brand 33 mm PVDF syringe filter (0.45 µm). The clear filtrate was divided into 6 mL portions that were placed into 20 mL scintillation vials. The scintillation vials were sealed tightly with Teflon-lined caps and placed in a 120 ºC oven for 24 h.7 The vials were then removed from the oven, and the mixture was allowed to cool to room temperature. The mother liquor was decanted away from the colorless needle-like crystals, and the crystals were washed with DMF (4 x 10 mL). The crystals were then dried at room temperature for 20 h under high vacuum. The average yield was 55%.

Synthesis of ZJU-28-1a

[Rh(CH3CN)2(COD)]BF4 (28 mg, 0.074 mmol) and DMF (2 mL) were combined in a 4 mL scintillation vial, with no precaution to exclude air, followed by the addition 1,2-bis(diphenylphosphino)ethane (29 mg, 0.074 mmol). The resulting solution was allowed to stand for 30 min. At this time, the solution was added to a suspension of ZJU-28 (100 mg) in DMF (3 mL) in a separate 20 mL scintillation vial. The vial was capped and placed in an orbital shaker for 3 d. The mother liquor was then decanted away from the crystals, and the crystals were washed with fresh DMF until the washings were colorless (~4 x 10 mL DMF). The metal-impregnated MOF was then dried at room temperature under high vacuum for 20 h. The material was analyzed by ICP-OES for Rh content and by PXRD for crystallinity.

Synthesis of ZJU-28-1b

ZJU-28 (100 mg) was suspended in DMF (3 mL) in a 20 mL scintillation vial. A solution of [Rh(CH3CN)2COD]BF4 (7.0 mg, 0.019 mmol) in DMF (2 mL) was added to the MOF suspension. The vial was capped and placed in an orbital shaker for 1 d. The mother liquor was then decanted away from the crystals, and the crystals were washed with fresh DMF until the washings were colorless (~4 x 10 mL DMF). The metal-impregnated MOF was then dried at room temperature under high vacuum for 20 h. The material was analyzed by ICP-OES for Rh content and by PXRD for crystallinity.

Determination of wt % metal uptake by ZJU-28.

1-2 mg of MOF were digested in 10% NaOH (1 mL) and diluted with H2O such that the final volume was 10 mL. This solution was subjected to ICP-OES analysis and the wt % uptake of the rhodium was determined by comparison to the wt% indium (In) using the following equation:

𝑤𝑡%  𝑅ℎ = (𝑤𝑡%  𝐼𝑛)  𝑝𝑝𝑚  𝑅ℎ𝑝𝑝𝑚  𝐼𝑛

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where wt% In = 16.5%, as determined from the molecular formula of ZJU-28

III. Catalytic Hydrogenation Procedures

Hydrogenation of 1-octene catalyzed by MIL-101-SO3-1a in neat 1-octene

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner were added MIL-101-SO3-1a (4.3 mg, 0.0013 mmol [Rh], 0.20 mol %) and 1-octene (1 mL, 6.4 mmol). The vessel was sealed, pressurized with 1 bar H2, and then vented via a pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 75 ºC (internal temperature). After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented and opened, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as a standard, and the yield of n-octane was determined using gas chromatography.

Catalyst recycling for hydrogenation of 1-octene catalyzed by MIL-101-SO3-1a in neat 1-octene

The MIL-101-SO3-1a remaining in the pressure vessel was washed with 1-octene (4 x 1 mL). After the final wash, fresh 1-octene was added. The vessel was sealed, and the hydrogenation reaction was conducted as described above. Additionally the catalyst was analyzed by PXRD after four additional recycles (see Figure S2).

Hydrogenation of 1-octene catalyzed by ZJU-28-1a in neat 1-octene

To a 50 mL stainless steel pressure vessel was added ZJU-28-1a (4.0 mg, 0.0013 mmol [Rh], 0.020 mol %) and 1-octene (1 mL, 6.4 mmol). The vessel was sealed, pressurized with 1 bar H2, and then vented via a pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 75 ºC (internal temperature). After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented and opened, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as a standard, and the yield of n-octane was determined using gas chromatography.

Catalyst recycling for hydrogenation of 1-octene catalyzed by ZJU-28-1a in neat 1-octene

The ZJU-28-1a remaining in the pressure vessel was washed with 1-octene (4 x 1 mL). After the final wash, fresh 1-octene was added. The vessel was sealed, and the reaction was conducted as described above. Additionally the catalyst was analyzed by PXRD after four additional recycles (see Figure S3).

Synthesis of Merrifield resin-supported alkene

To a 50 mL round bottom flask was added KOH (1.00 g, 17.8 mmol, 9.50 equiv) in DMF (20 mL). 5-Hexen-1-ol (1.96 g, 19.6 mmol, 10.4 equiv) was added to the flask, and the solution immediately turned yellow. The mixture was stirred for 1 h at room temperature, the unreacted KOH was removed by filtration, and Merrifield resin (1.00 g, 1.80 mmol,

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1.00 equiv) was added to the reaction solution. The reaction mixture was stirred for 1.5 h at room temperature. The resin was then transferred to a 50 mL conical centrifuge tube and centrifuged at 4000 rpm for 5 min. The resulting pellet was washed with DMF (3 x 25 mL) and EtOH (1 x 25 mL), and after each wash the pellet was centrifuged at 4000 rpm for 5 min. After the final wash, the pellet was dried at room temperature under high vacuum for 16 h. The functionalized resin was characterized by Raman spectroscopy.

Hydrogenation of solid-supported 5-hexen-1-ol catalyzed by MIL-101-SO3-1a

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added ZJU-28-1a (4.3 mg, 0.0013 mmol [Rh], 0.34 mol %), the Merrifield resin-supported alkene (0.20 g, 0.38 mmol), and acetone (1 mL). The vessel was sealed, pressurized with 1 bar H2, and then vented via a pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 75 ºC (internal temperature). After 48 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, and the Merrifield resin was removed (leaving the MOF behind). Analysis of the Merrifield resin by Raman spectroscopy showed that the olefin had not been hydrogenated (see Figure S8).

Hydrogenation of solid-supported 5-hexen-1-ol catalyzed by ZJU-28-1a in acetone

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added ZJU-28-1a (4.0 mg, 0.0013 mmol [Rh], 0.34 mol %), the Merrifield resin-supported alkene (0.20 g, 0.38 mmol), and acetone (1 mL). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 75 ºC (internal temperature). After 48 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, and the Merrifield resin was removed (leaving the MOF behind). Analysis of the Merrifield resin by Raman spectroscopy showed that the olefin had not been hydrogenated. This experiment was originally reported in ref. 2.

Hydrogenation of solid-supported 5-hexen-1-ol catalyzed by 1a in acetone

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added a pre-formed 0.0026M solution of [Rh(dppe)(COD)]BF4 (1a) in acetone (0.50 mL, 0.0013 mmol, 0.34 mol %). The Merrifield resin-supported alkene (0.20 g, 0.38 mmol) and acetone (0.5 mL) were then added, and the vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 75 ºC (internal temperature). After 48 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, and the Merrifield resin was removed and analyzed by Raman spectroscopy, which indicated that the olefin had been hydrogenated to alkane. This experiment was originally reported in ref. 2.

Hydrogenation of 1-octene catalyzed by MIL-101-SO3-1a in neat 1-octene under high pressure Raman conditions

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To a 50 mL stainless steel pressure vessel equipped with a Raman probe (see Figure S9 for picture) was added MIL-101-SO3-1a (43.0 mg, 0.013 mmol [Rh], 0.020 mol %) and 1-octene (10 mL, 64 mmol). and the vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 65 bar H2 and heated at 75 ºC (internal temperature). Raman spectra were collected every 10 minutes once the vessel reached 75 ºC. Reaction was monitored as a function of 1-octene (peak at 1643 cm-1) consumption as compared to an internal standard. After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as an internal standard, and the yield of reaction was independently verified using gas chromatography.

Catalyst recycling for hydrogenation of 1-octene catalyzed by MIL-101-SO3-1a in neat 1-octene under high pressure Raman conditions

The MIL-101-SO3-1a remaining in the pressure vessel was washed with 1-octene (4 x 10 mL). After the final wash, fresh 1-octene was added. The vessel was sealed, and the reaction was conducted as described above.

Hydrogenation of 1-octene catalyzed by ZJU-28-1a in neat 1-octene under high pressure Raman conditions

To a 50 mL stainless steel pressure vessel equipped with a Raman probe (see Figure S9 and S10 for picture) was added ZJU-28-1a (40.0 mg, 0.013 mmol [Rh], 0.020 mol %) and 1-octene (10 mL, 64 mmol). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 65 bar H2 and heated at 75 ºC (internal temperature). Raman spectra were collected every 10 minutes once the vessel reached 75 ºC. The reaction was monitored as a function of 1-octene consumption by utilizing the WiRE 3.4 software package’s curve fitting analysis for the peak at 1643 cm-

1 (representative of the double bond in 1-octene). After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as an internal standard, and the yield of reaction was independently verified using gas chromatography.

Catalyst recycling for hydrogenation of 1-octene catalyzed by ZJU-281a in neat 1-octene under high pressure Raman conditions

The ZJU-28-1a remaining in the pressure vessel was washed with 1-octene (4 x 10 mL). After the final wash, fresh 1-octene was added. The vessel was sealed, and the reaction was conducted as described above.

Hydrogenation of 2,3-dimethylbutene catalyzed by MIL-101-SO3-1a in neat 2,3-dimethylbutene

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner were added MIL-101-SO3-1a (4.3 mg, 0.0013 mmol [Rh], 0.0030 mol %) and 2,3-dimethylbutene (4.6 mL, 38.4 mmol). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air.

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The vessel was then pressurized with 75 bar H2 and heated at 100 ºC (internal temperature). After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as a standard, and the yield of 2,3-dimethylbutane was determined using gas chromatography.

Catalyst recycling for hydrogenation of 2,3-dimethylbutene catalyzed by MIL-101-SO3-1a in neat 2,3-dimethylbutene

The MIL-101-SO3-1a remaining in the pressure vessel was washed with 2,3-dimethylbutene (4 x 4 mL). After the final wash, fresh 2,3-dimethylbutene was added. The vessel was sealed, and the reaction was conducted as described above. Additionally the catalyst was analyzed by PXRD after four additional recycles (see Figure S4).Hydrogenation of 2,3-dimethylbutene catalyzed by MIL-101-SO3-1b in neat 2,3-dimethylbutene

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner were added MIL-101-SO3-1b (8.1 mg, 0.0013 mmol [Rh], 0.0030 mol %) and 2,3-dimethylbutene (4.6 mL, 38.4 mmol). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 75 bar H2 and heated at 100 ºC (internal temperature). After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as a standard, and the yield of 2,3-dimethylbutane was determined using gas chromatography.

Catalyst recycling for hydrogenation of 2,3-dimethylbutene catalyzed by MIL-101-SO3-1b in neat 2,3-dimethylbutene

The MIL-101-SO3-1b remaining in the pressure vessel was washed with 2,3-dimethylbutene (4 x 4 mL). After the final wash, fresh 2,3-dimethylbutene was added. The vessel was sealed, and the reaction was conducted as described above. Additionally the catalyst was analyzed by PXRD after four additional recycles (see Figure S5).

Hydrogenation of 2,3-dimethylbutene catalyzed by ZJU-28-1a in neat 2,3-dimethylbutene

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added ZJU-28-1a (4.0 mg, 0.0013 mmol [Rh], 0.0030 mol %) and 2,3-dimethylbutene (4.6 mL, 38.4 mmol). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 75 bar H2 and heated at 100 ºC (internal temperature). After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as a standard, and the yield of 2,3-dimethylbutane was determined using gas chromatography.

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Catalyst recycling for hydrogenation of 2,3-dimethylbutene catalyzed by ZJU-28-1a in neat 2,3-dimethylbutene

The ZJU-28-1a remaining in the pressure vessel was washed with 2,3-dimethylbutene (4 x 4 mL). After the final wash, fresh 2,3-dimethylbutene was added. The vessel was sealed, and the reaction was conducted as described above. Additionally the catalyst was analyzed by PXRD after four additional recycles (see Figure S6).Hydrogenation of 2,3-dimethylbutene catalyzed by ZJU-28-1b in neat 2,3-dimethylbutene

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added ZJU-28-1b (6.2 mg, 0.0013 mmol [Rh], 0.0030 mol %) and 2,3-dimethylbutene (4.6 mL, 38.4 mmol). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 75 bar H2 and heated at 100 ºC (internal temperature). After 24 h, the vessel was cooled to 0 ºC in an ice bath. The vessel was vented, the solution was removed (leaving the MOF behind), ethyl benzene was added to the solution as a standard, and the yield of 2,3-dimethylbutane was determined using gas chromatography.

Catalyst recycling for hydrogenation of 2,3-dimethylbutene catalyzed by ZJU-28-1b in neat 2,3-dimethylbutene

The ZJU-28-1b remaining in the pressure vessel was washed with 2,3-dimethylbutene (4 x 4 mL). After the final wash, fresh 2,3-dimethylbutene was added. The vessel was sealed, and the reaction was conducted as described above. Additionally the catalyst was analyzed by PXRD after four additional recycles (see Figure S7).

Hydrogenation of tetraallylcalix[4]arene (2a) catalyzed by MIL-101-SO3-1a in C6D6

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added MIL-101-SO3-1a (4.3 mg, 0.0013 mmol [Rh], 0.54 mol %), tetraallylcalix[4]arene (2a, 0.05 g, 0.06 mmol, 0.24 eq alkene), and C6D6 (1 mL). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 35 ºC (internal temperature). After 24 h, the vessel was allowed to cool to room temperature. The vessel was vented, and the reaction was analyzed by 1H NMR spectroscopy (see Figure S11). The 1H NMR spectrum of the crude reaction mixture showed complete conversion of the alkene resonances to the corresponding alkane resonances.

Hydrogenation of tetraallylcalix[4]arene (2a) catalyzed by ZJU-28-1a in C6D6

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added ZJU-28-1a (4.0 mg, 0.0013 mmol [Rh], 0.54 mol %), tetraallylcalix[4]arene (2a, 0.05 g, 0.06 mmol, 0.24 eq alkene), and C6D6 (1 mL). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 35 ºC (internal temperature). The vessel was vented, and the reaction was analyzed by

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1H NMR spectroscopy (see Figure S11). The 1H NMR spectrum of the crude reaction mixture showed that no reaction had occurred.

Hydrogenation of tetraallylcalix[4]arene (2a) catalyzed by 1a in C6D6

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added a pre-formed 0.0026 M solution of [Rh(dppe)(COD)]BF4 in C6D6 (0.50 mL, 0.0013 mmol, 0.54 mol %). Calixarene (2a, 0.05 g, 0.06 mmol, 0.24 eq alkene) and C6D6 (0.5 mL) were then added. The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 35 ºC (internal temperature). After 24 h, the vessel was vented, and the reaction was analyzed by 1H NMR spectroscopy (see Figure S11). The 1H NMR spectrum of the crude reaction mixture showed complete reaction of the alkenes to the corresponding alkanes.

Hydrogenation of octaallylcalix[8]arene (2b) catalyzed by MIL-101-SO3-1a in C6D6

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added MIL-101-SO3-1a (4.3 mg, 0.0013 mmol [Rh], 0.54 mol %), octaallylcalix[8]arene (2b, 0.05 g, 0.03 mmol, 0.24 eq alkene), and C6D6 (1 mL). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 35 ºC (internal temperature). After 24 h, the vessel was vented, and the reaction was analyzed by 1H NMR spectroscopy (see Figure S12). The 1H NMR spectrum of the crude reaction mixture showed 52 turnovers to hydrogenated product.

Hydrogenation of octaallylcalix[8]arene (2b) catalyzed by ZJU-28-1a in C6D6

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added ZJU-28-1a (4.0 mg, 0.0013 mmol [Rh], 0.54 mol %), octaallylcalix[8]arene (2b, 0.05 g, 0.03 mmol, 0.24 eq alkene), and C6D6 (1 mL). The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 35 ºC (internal temperature). After 24 h, the vessel was vented, and the reaction was analyzed by 1H NMR spectroscopy (see Figure S12). The 1H NMR spectrum of the crude reaction mixture showed that the ratio of aromatic protons to a selected geminal alkene proton was unchanged (2:1), which indicates that no hydrogenation of the alkene had occurred.

Hydrogenation of octaallylcalix[8]arene (2b) catalyzed by 1a in C6D6

To a 50 mL stainless steel pressure vessel fitted with a Teflon liner was added a pre-formed 0.0026 M solution of [Rh(dppe)(COD)]BF4 (1a) in C6D6 (0.50 mL, 0.0013 mmol, 0.54 mol %). Calixarene (2b, 0.05 g, 0.03 mmol, 0.24 eq alkene) and C6D6 (0.5 mL) were then added. The vessel was sealed, pressurized with 1 bar H2, and then vented via pressure release valve. This process was repeated twice to remove any residual air. The vessel was then pressurized with 10 bar H2 and heated at 35 ºC (internal temperature). After 24 h, the vessel was vented, and the reaction was analyzed by 1H NMR spectroscopy (see Figure S12). The 1H NMR spectrum of the crude reaction

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mixture showed complete conversion of the alkene resonances to the corresponding alkane resonances.

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IV Supplemental Figures

1) PXRD Data

Figure S1. PXRD of MIL-101-SO3 and MIL101-SO3-1a and 1b

Figure S2. PXRD of MIL-101-SO3-1a after five recycles (1-octene hydrogenation)

MIL-­‐101-­‐SO3-­‐1b

MIL-­‐101-­‐SO3-­‐1a

MIL-­‐101-­‐SO3

MIL-­‐101-­‐SO3-­‐1a,  post  5  reactions

MIL-­‐101-­‐SO3-­‐1a

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Figure S3. PXRD of ZJU-28-1a after five recycles (1-octene hydrogenation)

Figure S4. PXRD of MIL-101-SO3-1a after five recycles (2,3-dimethylbutene hydrogenation)

MIL-­‐101-­‐SO3-­‐1a,  post  5  reactions

MIL-­‐101-­‐SO3-­‐1a

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Figure S5. PXRD of MIL-101-SO3-1b after five recycles (2,3-dimethylbutene hydrogenation)

Figure S6. PXRD of ZJU-28-1a after five recycles (2,3-dimethylbutene hydrogenation)

MIL-­‐101-­‐SO3-­‐1b,  post  5  reactions

MIL-­‐101-­‐SO3-­‐1b

ZJU-­‐28-­‐1a

ZJU-­‐28-­‐1a,  post  5  reactions

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Figure S7. PXRD of ZJU-28-1b after five recycles (2,3-dimethylbutene hydrogenation)

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2) Raman Data

Figure S8. Representative Raman Analysis of three-phase test: Hydrogenation of solid-supported 5-hexen-1-ol catalyzed by MIL-101-SO3-1a

Figure S9. Experimental setup for high pressure Raman experiments

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Figure S10. Representative Raman data from high pressure catalysis experiments

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3) NMR Data

Figure S11. Representative 1H NMR spectra for tetraallylcalix[4]arene hydrogenation (1) NMR of tetraallylcalix[4]arene (2a), (2) NMR of reaction mixture post 24 h with 1a as catalyst, (3) NMR of reaction mixture post 24 h with ZJU-28 1a as catalyst (d) NMR of reaction mixture post 24 h with MIL-101-SO3-1a as catalyst

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Figure S12. Representative 1H NMR spectra for octaallylcalix[8]arene hydrogenation reactions (1) NMR of octaallylcalix[4]arene (2a), (2) NMR of reaction mixture post 24 h with 1a as catalyst, (3) NMR of reaction mixture post 24 h with ZJU-28 1a as catalyst (d) NMR of reaction mixture post 24 h with MIL-101-SO3-1a as catalyst

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V References

1. Choi, S. B.; Seo, M. J.; Cho, M.; Kim, Y.; Jin, M. K.; Jung, S-Y, Choi, J-S; Ahn, W-S; Rowsell, J. L. C.; Kim, J. Cryst. Growth and Des. 2007, 7, 2290-2293.

2. Genna, D. T.; Wong-Foy, A. G.; Matzger, A. J.; Sanford, M. S. J. Am. Chem. Soc. 2013, 135, 10586-10589.

3. Bitter, I.; Grün, A.; Ágai, B.; Tôke, L. Tetrahedron 1995, 51, 7835-7840 4. Wang, W-G.; Zheng, Q-Y; Huang, Z-T. Synth. Commun. 1999, 29, 3711-3718. 5. Procedure modified from: Akiyama, G.; Matsuda, R.; Sato, H.; Takata, M.; Kitagawa,

S. Adv. Mater. 2011, 23, 3294-3297. 6. Yu J.; Cui, Y.; Wu, C.; Yang, Y.; Wang, Z.; O’Keefe, M.; Chen, B.; Qian, G. Angew.

Chem. Int. Ed. 2012, 51, 10542-10545. 7. Note: In our hands, when this reaction was run at 130 ºC as reported in ref #1, the

product was a white crystalline powder rather than needle-like crystals.