Supporting Information

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1 Highly Dispersed Palladium(II) in a Defective MOF: Application to C-H Activation and Functionalization Tae-Hong Park, Amanda Hickman, Kyoungmoo Koh, Stephen Martin, Antek Wong- Foy, Melanie S. Sanford, * Adam J. Matzger * Department of Chemistry and Macromolecular Science and Engineering Program, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan Supporting Information Contents 1. Synthesis and characterization 2. N 2 isotherm measurements 3. Pd(II)@MOF-5(O h )-catalyzed phenylation of naphthalene 4. Full list of authors of reference 5b 5. Disclaimer 6. References S 1

2 1. Synthesis and Characterization Synthesis of MOF-5(O h ) and impregnation of palladium H 2 BDC (0.300 g 1.81 mmol), H 3 BTB ( g, mmol), and Zn(NO 3 ) 2 6H 2 O (1.50 g, 5.04 mmol) were dissolved in DEF (50 ml). The mixture was heated at 100 C for 24 h. The mother liquor was decanted and the crystals were washed with DMF three times and CH 2 Cl 2 twice. The MOF-5(O h ) crystals were immersed in a solution of Pd(OAc) 2 (25.0 mg, mmol) in 12.5 ml CH 2 Cl 2 (8.91 mm) and the mixture was slowly shaken using a shaker for 2 d. Then a fresh Pd(OAc) 2 solution was replenished and the mixture was shaken for another 2 d. The solution was decanted and the crystals were washed with CH 2 Cl 2 three times and immersed in CH 2 Cl 2 for 2 days during which fresh CH 2 Cl 2 was replenished three times to afford brown Pd(II)@MOF-5(O h ) crystals. For reduction of Pd, Pd(II)@MOF-5(O h ) was immersed in DMF (5.0 ml). The solution of NaBH 4 (30.0 mg, mmol) in DMF (10 ml) was added and the mixture was shaken for 2 h. After the solution was decanted, the black crystals were washed with DMF three times and immersed in CH 2 Cl 2 for 24 h during which fresh CH 2 Cl 2 was replenished three times. The crystals were dried under vacuum at room temperature for 20 h (yield 370 mg). Figure S1. PXRD data for MOF-5, Pd(II)@MOF-5(O h ), and Pd@MOF-5(O h ). S 2

3 Figure S2. 1 H NMR spectra of 10% BTB loaded MOF-5(O h ) (bottom) and Pd(II)@MOF-5(O h ) (top) in DMSO-d 5 containing DCl and benzne-d 6. S 3

4 Figure S3. FT-IR spectra of MCPs. The absence of carbonyl peaks corresponding to carboxylic acids is consistent with the notion that deprotonation of the ligands, including those with dangling coordinating functionality, is completed during synthesis. S 4

5 Figure S4. Optical microscopy images of cross sectioned crystals. Left, and right, Reddish brown color from Pd(II) (left) and dark brown color from Pd metal (right) are spread uniformly through internal slices from the bulk crystals. This indicates that the defects introduced from BTB are uniformly distributed within the crystals and functionalized throughout the crystal. Figure S5. Core-shell type crystals (core, shell, MOF-5). Condition: crystals were placed in a DEF solution containing H2BDC and Zn(NO3)2 6H2O, and the mixture was heated at 80 C for 12 h.1 Scale bar: 0.5 mm. S 5

6 2. N 2 isotherm measurements N 2 adsorption isotherms were measured by a volumetric method at 77 K on a NOVA 4200 by Quantachrome Instruments (Boynton Beach, Florida, USA). Ultra-high purity N 2 (99.999%) was purchased from Cryogenic Gasses and used as received. The pressure range of P/P was used for the measurement of the surface area. Figure S6. N 2 isotherms and BET surface areas. Open symbols represent an adsorption branch and closed symbols a desorption branch. S 6

7 3. phenylation of naphthalene General Procedure for Pd-catalyzed phenylation of naphthalene 2 Reactions were prepared in 4 ml screw cap vials. Each vial was charged with [Ph 2 I]BF 4 (27.1 mg, mmol, 1 equiv), naphthalene (47.1 mg, mmol, 5 equiv), Pd(II)@MOF-5 (17.0 mg, 3.68 μmol Pd, 5 mol % Pd) and nitrobenzene (0.75 ml). The Pd content within Pd(II)@MOF-5(O h ) was 2.3 wt % determined by ICP-OES. The vials were fitted with Teflon-lined caps and slowly shaken at 120 C in a preheated aluminum block for an appropriate time, and then cooled to room temperature. Hexadecane (22 μl, mmol) was added to the vials as an internal standard. The reaction mixture was filtered through a Celite plug, and the plug was washed with ethyl acetate. The filtrate was diluted to approximately 10 ml and analyzed by GCMS. Yields and selectivities were determined by comparison to calibration curves. Table S1. Pd(II)-catalyzed phenylation of naphthalene a Conditions: Pd catalyst (5 mol %), naphthalene (5 equiv), Ph 2 IBF 4 in NO 2 Ph at 120 C. S 7

8 Figure S7. (a) PXRD study of solid obtained from filtration of the reaction mixture of the 5(O h )-catalyzed phenylation of naphthalene in nitrobenzene at 120 C. (b) TEM image of solid obtained from the 12 h reaction mixture (scale bar: 20 nm). S 8

9 4. Full list of authors of reference 5b Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C.; Chang, J.-S.; Hwang, Y. K.; Marsaud, V.; Bories, P.-N.; Cynober, L.; Gil, S.; Férey, G.; Couvreur, P.; Gref, R. Nat. Mater. 2010, 9, Disclaimer This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. 6. References (1 ) Koh, K.; Wong-Foy, A. G.; Matzger, A. J. Chem. Commun. 2009, (2 ) Hickman, A. J.; Sanford, M. S. ACS Catal. 2011, 1, S 9