Electronic Supplementary Material

Metal-organic layers as reusable solid fluorination reagents andheterogeneous catalysts for aromatic fluorination Wenjie Shi1,2, Lingzhen Zeng1, Lingyun Cao1, Ying Huang1, Cheng Wang1 (), and Wenbin Lin

2

1 State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National

Engineering Laboratory for Green Chemical Production of Alcohols, Ethers and Esters, Department of Chemistry, College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005, China

2 Department of Chemistry, University of Chicago, Chicago, IL 60637, USA Supporting information to https://doi.org/10.1007/s12274-020-2698-8

Table of Contents Section S1. Materials and Methods Section S2. Synthetic Conditions for Pd-MOL-X and F-Pd-MOL-X Section S3. Preparation of Pd(TPY-OMe)(X) Complexes Section S4. Preparation of Substrates for Fluorination Section S5. Procedure for F-Pd-MOL-phenCl as a solid reagent, [PdII(TPY-OMe)(phenCl)]2+ as homogenous catalyst and

Pd-MOL-phenCl as heterogeneous catalyst in aromatic fluorination Section S6. Procedure for F-Pd-MOL-phenCl as a solid reagent, [PdII(TPY-OMe)(phenCl)]2+ as homogenous catalyst and

Pd-MOL-phenCl as heterogeneous catalyst in aromatic fluorination Section S7. DFT calculation of 19F- NMR chemical shifts Section S8. C-H fluorination reactions Section S9. Extended x-ray absorption fine structure (EXAFS) of Pd-MOL-X and F-Pd-MOL-X Section S10. NMR study of the reactive center in the F-Pd-MOL-phenCl

Section S1 Materials and Methods Reagents were commercially available and used without further purification unless otherwise indicated. The powder X-ray diffraction data were collected on Agilent SuperNova, Rigaku and Bruker D8 Venture diffractometers using Cu Kα radiation sources (λ = 1.54178 Å). Transmission electron microscopy images were obtained on JEOL 2100 High Resolution Transmission Electron Microscopy. AFM images were taken on a Bruker Multimode V. 1H-NMR spectra were recorded on a Bruker NMR 500 DRX spectrometer at 500 MHz and referenced to the proton resonance resulting from incomplete deuteration of the CD3CN-d6 (δ 1.94), and 19F-NMR spectra were recorded on Bruker NMR 400MHz Avance II spectromter or Bruker NMR 600MHz Avance III HD spectromter, with the unified scale using solvent as a reference compound for 19F-NMR. 19F-NMR chemical shifts of resulting reaction mixtures are reported with an added compound as the internal standard: 2-Fluorobenzotrifluoride, δ= -61.2 ppm and δ= -116.3ppm. and 4-Fluorobenzotrifluoride, δ= -61.7 ppm and δ= -109.2ppm. X-ray photoelectron spectroscopy (XPS) measurements were carried out with a Qtac-100 LEISS-XPS spectrometer with a hemispherical electron energy analyser and a home-made reaction chamber. Monochromatic Al Kα X-ray source (1486.6 eV, anode operating at 300 W) was used as the excitation source. The energy analysis error of the measurement was ±0.2 eV for both binding energy and Auger energy. The binding energies in all the spectra were calibrated according to C 1s peak at 284.6 eV. We referred the XPS binding energies to the NIST XPS database (https://srdata.nist.gov/xps/main_search_menu.aspx).

Section S2 Synthetic Conditions for Pd-MOL-X and F-Pd-MOL-X

S2.1 Synthetic conditions for MOL The synthesis of MOL [Hf6O4(OH)4(HCO2)6(TPY)2] followed the procedures in our previous work [S1]. A mixture of HfCl4 (35 mg) and H3TPY (32 mg) was dissolved in a mixture of DMF (12.5 mL), HCOOH (2.5 mL) and water (700 μL) in Pyrex vials, and kept at 120 oC for 2 days. White precipitates were obtained and washed with DMF for three times.

Address correspondence to wangchengxmu@xmu.edu.cn

Nano Res.

| www.editorialmanager.com/nare/default.asp

2

Figure S1 PXRD pattern (a),Transmission Electron Microscopy (TEM) image (b), Atomic force microscopy (AFM) image (b) and height profile (c) of MOL without Pd functionalization.

S2.2 Preparation of Pd-MOL-X The MOL (5mg, 2 μmol) was metalated with Pd(OAc)2 (1.05 equiv. relative to TPY) overnight in MeCN and then washed with MeCN three times, affording an orange suspension Pd-MOL. To this Pd-MOL suspension was added HBF4•OEt2 (2.05 equiv.) and 2-Chloro-1,10-phenanthroline (1 mg, 4 μmol, 4mol%). The reaction mixture was stirred vigorously for 10 mins and washed with acetonitrile three time to obtain Pd-MOL-phenCl. When the 1,10-phenanthroline, 2-methyl-1,10-phenanthroline or 2,2'-bipyridine are used, Pd-MOL-phen, Pd-MOL-phenCH3, or Pd-MOL-bpy are obtained, respectively, following similar procedure.

S2.2 Preparation of F-Pd-MOL-X The MOL (10mg, 4 μmol) was treated with DMAP (8 equiv. relative to TPY) first and then metalated with Pd(OAc)2 (0.5 equiv. relative to TPY). After that, we follow the same procedure to synthesize Pd-MOL-phenCl. The Pd-MOL-phenCl was treated with Selectfluor (2 equiv. relative to Pd) in MeCN in glovebox. The reaction took around 1 minute under room temperature. Then the solid was washed with MeCN twice. When the additive was 1,10-phenanthroline, F-Pd-MOL-phen was obtained following similar procedure.

Section S3 Preparation of Pd(TPY-OMe)(X) Complexes

S3.1 Preparation of TPY-OMe

To a methanol solution (50 mL) of (4’-(4-benzoate)-(2,2’,2’’-terpyridine)-5,5’’-dicarboxylate) (TPYTC) (100 mg, 0.23 mmol, 1 equiv.) was added H2SO4 (2.3mL, 2.5 mmol, 10 equiv.) dropwise in ice bath. After that, the mixture was refluxed for 8 hours at 80 oC. Water (30 mL) and NH3·H2O were then added to the mixture to adjust the pH to 7. The product was then extracted with CH2Cl2, dried over sodium sulfate, filtered, and concentrated in vacuo. The TPY-OMe (70 mg, 70%) was then obtained.

Figure S2 1H-NMR spectra of TPY-OMe.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

3

S3.2 Preparation of [PdII(TPY-OMe)(MeCN)]2+ Precursor

Following a procedure adapted from a previous publication [S2]: To a MeCN solution of Pd(OAc)2 (29 mg, 0.13 mmol, 1 equiv.) (4.7 mL, c = 0.07 M) at 23 ºC was added TPY-OMe (60 mg, 0.13 mmol, 1 equiv.). The reaction mixture was stirred for 20 minutes to afford an orange slurry. To this slurry was added HBF4•OEt2 (29 μL, 0.26 mmol, 2 equiv.) via a syringe. The reaction mixture was stirred vigorously for 30 min, at which point a tan suspension was observed and Et2O (18 mL) was added. The solids were collected by filtration and washed with Et2O (20 mL). The combined solids were then dried under vacuum to afford the title compound as a pale tan solid (55 mg, 0.12 mmol, 92% yield).

Section S4 Preparation of Substrates for Fluorination

Following a published procedure [S3]: A mixture of ciprofibrate (350 mg, 1.21 mmol, 1 equiv.), n-butanol (220 μL, 2.4 mmol, 2 equiv.), 4-dimethylamino pyridine (30mg, 240 umol, 20 mol%), and N,N’-dicyclohexylcarbodiinid (250mg, 1.2 mmol, 1.0 equiv.) in dry CH2Cl2 (10 mL) was stirred for 11 hours at room temperature. The mixture was diluted with dichloromethane and washed with saturated aqueous NaHCO3 solution. The organic phase was dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by column chromatography on silica gel (hexane/ ethyl acetate (50:1 to 30:1 (v/v)) to provide butyl ciprofibrate (345 mg, 1.00 mmol, 83%) as a colorless oil.

NMR spectroscopy

Figure S3 1H NMR spectra of butyl ciprofibrate.

Nano Res.

| www.editorialmanager.com/nare/default.asp

4

Figure S4 13C NMR spectra of butyl ciprofibrate.

Section S5 Procedure for F-Pd-MOL-phenCl as a solid reagent, [PdII(TPY-OMe)(phenCl)]2+ as homogenous catalyst and Pd-MOL-phenCl as heterogeneous catalyst in aromatic fluorination

S5.1 Procedure for F-Pd-MOL-phenCl as a solid reagent in C-H fluorination

Under N2 atmosphere, arene 1 (2 μmol, 1 equiv), F-Pd-MOL-phenCl (10 mg, 2 μmol of Pd, 1 equiv), and acetonitrile (1 mL) were added into a 25mL round flask in glovebox. The resulting reaction mixture was stirred at 50 oC for 50 h and the yield was determined by integrations in 19F-NMR, referring to an internal standard.

S5.2 Procedure for [PdII(TPY-OMe)(phenCl)]2+ as homogenous catalyst in C-H fluorination

[PdII(TPY-OMe)(MeCN)]2+ (4.43 mg, 4 μmol, 4 mol% ) and 2-chlorophenanthroline (2.8 mg, 4 μmol, 4 mol%) was added to a 25 mL round bottom flask containing a solution of Selectflour (140 mg, 0.4 mmol, 4 equiv.) and the arene (0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 2-flourobenzotrifluoride (6.5 mg, 5 μL, 40 μmol, 0.4 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR relative to the internal standard.

S5.3 Procedure for Pd-MOL-phenCl as heterogenous catalyst in C-H fluorination

Under N2 atmosphere, arene 1 (0.1 mmol, 1.00 equiv), Selectflour (35mg, 0.1 mmol or 70 mg, 0.2 mmol), and acetonitrile (1 mL) were added in a 25 mL round bottom flask. To a separate 5mL vial, Pd-MOL-phenCl (5 mg, 2 μmol, 2 mol%) and acetonitrile (2 mL) were added. The catalyst suspension was added to the mixture of arene and Selectfluor (final c=0.05 M). The resulting reaction mixture was stirred at 50 oC or 25 oC for 36 h and the yield was determined by integrations in 19F-NMR relative to the internal standard.

S5.4 Reaction without a catalyst: Under N2 atmosphere, a 25 mL round bottom flask was charged with Selectflour (35mg, 0.1 mmol or 70 mg, 0.2 mmol, 2 equiv. or 0.7 mg, 2 μmol, 1 equiv. ), the substrate (1 equiv.), and acetonitrile (2 mL, c = 0.05 M). The resulting reaction mixture was stirred under 50 oC for 36 hours. After that, 2-flourobenzotriflouride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by the integration in 19F-NMR relative to the internal standard.

Section S6 DFT calculation of 19F- NMR chemical shifts DFT calculations were performed using the Gaussian 09 (revision B.01) software package. All geometries were optimized using the B3LYP hybrid functional with the 6-31G(d) basis set. Isotropic NMR shielding tensors of fluorobenzene compounds were

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

5

calculated at the B3LYP level using the gauge-independent atomic orbital (GIAO) method, 6-31* basis set [S4]. Isotropic NMR shielding tensors of alkyl fluorides were calculated with the fluorobenzene compounds following similar method except using the 6-311 ** basis set [S5]. The chemical shifts (δ) were calculated from the shielding (σ) by

δ = σref – σcal where σref is the shielding of CFCl3 calculated by the same method. CFCl3 is a commonly used reference for 19F-NMR chemical

shifts. We calculated 19F-NMR chemical shifts of a series of fluorine-containing compounds to construct a standard curve.

Table S1 Summerization of 19F-NMR chemical shifts for fluorobenzenes.

ortho meta para number substituent

Experiment a / ppm Calculation b / ppm Experiment a / ppm Calculation b / ppm Experiment a / ppm Calculation b / ppm

1 CH3 -118.4 -122.98 -114.9 -123.4 -119.2 -127.1659 2 NO2 -119.7 -121.1932 -110 -116.1719 -103 -102.7605 3 COCl -109.5 -118.5658 - - - - 4 OH -138 -149.219 -113.2 -120.8621 -126.8 -135.4861 5 NH2 -136.3 -155.6419 -115.6 -124.2569 -129.7 -144.4875

All data are relative to CFCl3 (ppm), a Solvent is acetone, b Solvent is acetonitrile.

Table S2 19F-NMR chemical shifts of substrates in our work.

a b c d number name

experiment calculation experiment calculation experiment calculation experiment calculation

3 phenol

-138.24 ppm -134.44 ppm -126.37 ppm -124.87 ppm -105.9 ppm -104.66 ppm -98.1 ppm -98.2 ppm

- 4 2-phenylpyridine

-117.3 ppm -117.26 ppm -110.89 ppm -113.94 ppm -113.19 ppm -115.5 ppm - -

- - 6 diphenylmethane

-118.6 ppm -119.8 ppm -118.2 ppm -118.0 ppm - - - -

Table S3 Summerization of 19F-NMR chemical shifts for alkyl fluorides.

Structural formula

Experiment a -218 ppm -131 ppm -158 ppm -213 ppm -160 ppm -171 ppm -175 ppm -212 ppm Calculation b -213.6 ppm -134.4 ppm -154.4 ppm -214.0 ppm -153.0 ppm -179.4 ppm -166.1 ppm -209.7 ppm

aAll data were relative to CFCl3 (ppm), b Solvent is acetonitrile.

Table S4 19F-NMR chemical shifts of substrates in our work.

c d number name

Experiment / ppm Calculation / ppm Experiment / ppm Calculation / ppm

5 4-phenylcyclohexanone

-186.9 -183.1 -189.5 -185.9

Nano Res.

| www.editorialmanager.com/nare/default.asp

6

Figure S5 19F-NMR standard curve of fluorobenzene compounds.

Figure S6 19F-NMR standard curve of alkyl fluorides.

Section S7 C-H fluorination reactions

Table S5 Summerization of the fluorination results of using Pd-MOL-phenCl or [PdII(TPY-OMe)(phenCl)]2+ as catalysts and using F-Pd-MOL-phenCl as solid reagent.

Solid reagent Homogenous catalyst Heterogenous catalyst Number substrate

F-Pd-MOL-phenCl [PdII(TPY-OMe)(MeCN)]2+ Pd-MOL-phenCl Without catalyst

1 4-cyanobiphenyl 81% 97% 90% 0% 2 toluene 33% 31% 55% 0% 3 phenol 100% 75% 76% 13% 4 2-phenylpyridine 81% 54% 82% 0% 5 4-phenylcyclohexanone 81% 95% 62% 0% 6 diphenylmethane 100% 64% 68% 0% 7 4,6-dichloro-2,5-diphenylpyrimidine 7% 59% 30% 0% 8 butyl ciprofibrate 52% 21% 34% 0%

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

7

Table S6 Summerization of control experiments for catalysis

Number Condition Yield of substrate 1

1 MOL without Pd functionalization as the catalyst 0 % 2 Pd-MOL-phenCl without the treatment of HBF4·OEt2 17 %

S7.1 Reaction between 4-cyanobiphenyl and F-Pd-MOL-phen.

F-Pd-MOL-phen (10 mg, 2 μmol of Pd, 1 quive.) was added to a 25 mL round bottom flask containing 4-cyanobiphenyl 1 (0.36 mg, 2 μmol, 1 equiv.) in acetonitrile (1 mL). After stirring for 50 hours at 50 oC, 2-flourobenzotrifluoride (2.6 mg, 2 μL, 16 μmol, 8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR (0% yield).

Figure S7 19F-NMR spectra of products from fluorination reaction of 1 using F-Pd-MOL-phen as solid reagent. 0% yeild.

S7.2 Reuse test of F-Pd-MOL-phenCl F-Pd-MOL-phenCl (10 mg, 2 μmol of Pd, 1 equiv.) was added to a 25 mL round bottom flask containing 4-cyanobiphenyl 1 (0.36 mg, 2 μmol, 1 equiv.) in acetonitrile (1 mL). After stirring for 50 hours at 50 oC, 2-flourobenzotrifluoride (2.6 mg, 2 μL, 16 μmol, 8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR. The collected F-Pd-MOL-phenCl was then used in subsequent reaction runs. At each round, we regenerated the solid reagent following the previous steps of treatment with base (DMAP), phenCl and Selectfluor. The yield was determined by integrations in 19F-NMR. After each cycle, we also analysed the amount of leached Pd in the solution by ICP-MS.

Figure S8 Recycle test of F-Pd-MOL-phenCl as solid fluorination reagent.

Nano Res.

| www.editorialmanager.com/nare/default.asp

8

S7.3 Stability test of F-Pd-MOL-phenCl F-Pd-MOL-phenCl (10 mg, 2 μmol of Pd, 1 equiv. ) was kept in a MeCN solution for one day, a week, and 30 days, and then separated from the solution to a 25 mL round bottom flask containing 4-cyanobiphenyl 1 (0.36 mg, 2 μmol, 1 equiv.) in acetonitrile (1 mL). After stirring for 50 hours at 50 oC, 2-flourobenzotrifluoride (2.6 mg, 2 μL, 16 μmol, 8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR.

S7.4 Reactivity test of F-Pd-MOL-phenCl after exposure to air F-Pd-MOL-phenCl (10 mg, 2 μmol of Pd, 1 equiv. ) was kept in a MeCN solution and exposed to air for 3 mins, before added to a 25 mL round bottom flask containing 4-cyanobiphenyl 1 (0.36 mg, 2 μmol, 1 equiv.) in acetonitrile (1 mL). After stirring for 50 hours at 50 oC, 2-flourobenzotrifluoride (2.6 mg, 2 μL, 16 μmol, 8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR.

Table S7. Summerization of control experiments using F-Pd-MOL-phenCl as solid fluorination reagent

Number Condition Yield of substrate 1

1 F-Pd-MOL-phenCl was kept for 1 day 79% 2 F-Pd-MOL-phenCl was kept for 1 week 40 % 3 F-Pd-MOL-phenCl was kept for 30 days 20 % 4 F-Pd-MOL-phenCl was exposed to air for 3mins 11 %

S7.5 4-Cyano-2’-fluorobiphenyl (1a) and 4-cyano-4’-fluorobiphenyl (1b) (The 19F-NMR chemical shift was reported by previous literature3)

Figure S9 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 1. Top: 81% yield, 1a: 1b = 64: 36. Bottom; 0% yield. 1a: -119.4 ppm; 1b: -115.2 ppm.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

9

Figure S10 19F-NMR spectra of products from fluorination reaction of 1 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: yield: 90%, 1a:1b = 58:42. Bottom: yield:0%. 1a: -119.4 ppm; 1b: -115.2 ppm.

Figure S11 19F-NMR spectra of products from fluorination reaction of 1 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst, 97% yield. 1a: -119.4 ppm; 1b: -115.2 ppm.

Nano Res.

| www.editorialmanager.com/nare/default.asp

10

S7.5 2-Fluorotoluene (2a) and 4-fluorotoluene (2b)

Figure S12 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 2. Top: 33% yield, 2a: 2b = 50: 50. Bottom: 0% yield. 2a: -119.5ppm; 2b: -118.6 ppm.

Figure S13 19F-NMR spectra of products from fluorination reaction of 2 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: yield: 55%, 2a:2b = 45:55. Bottom: yield:0%. 2a: -119.5ppm; 2b: -118.6 ppm.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

11

Figure S14 19F-NMR spectra of products from fluorination reaction of 2 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst, 31% yield . 2a: -119.5ppm; 2b: -118.6 ppm.

S7.6 2-Fluorophenol (3a), 4-fluorophenol (3b), 2-fluorocyclohexa-2,5-diene-1,4-dione (3c) and 3-fluoro-4-hydroxycyclohexa- 2,5-dien-1-one (3d)

Figure S15 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 3. Top: 100% yield, 3a: 3b = 56: 44. Bottom: 18% yield. 3a: -138.3 ppm; 3b: -126.5 ppm.

Nano Res.

| www.editorialmanager.com/nare/default.asp

12

Figure S16 19F-NMR spectra of products from fluorination reaction of 3 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: yield: 76%, 3a:3b:3c:3d = 25:22:17:36. Bottom: yield: 13% yield, 3a:3b = 56:44. 3a: -138.3 ppm; 3b: -126.5 ppm; 3c: -105.9 ppm; 3d: -98.1 ppm.

Figure S17 19F-NMR spectra of products from fluorination reaction of 3 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst. 75% yield, 3a: 3b: 3d = 41:44:15. 3a: -138.3 ppm; 3b: -126.5 ppm; 3d: -98.1 ppm.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

13

S7.7 2-(2-Fluorophenyl) pyridine (4a), 2-(4-fluorophenyl) pyridine (4b) and 2-(3-fluorophenyl)pyridine (4c) (The 19F-NMR chemical shift was reported by previous literature3)

Figure S18 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 4. Top: 81% yield, 4a: 4c: = 73: 27. Bottom: 0% yield. 4a: -117.3 ppm; 4c: -113.2 ppm

Figure S19 19F-NMR spectra of products from fluorination reaction of 4 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: 82% yield, 4a:4b = 59:41. Bottom: 0% yield. 4a: -117.3 ppm; 4b: -110.9 ppm.

Nano Res.

| www.editorialmanager.com/nare/default.asp

14

Figure S20 19F-NMR spectra of products from fluorination reaction of 4 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst. 54% yield, 4a:4b = 67:33. 4a: -117.3 ppm; 4b: -110.9 ppm.

S7.8 4-(2-Fluorophenyl) cyclohexanone (5a), 4-(4-fluoropheyl)cyclohexanone (5b), 2-fluoro-4-phenylcyclohexan- 1-one (5c) and 3-fluoro-4-phenylcyclohexan- 1-one (5d) ( The 19F-NMR chemical shift was reported by previous literature3)

Figure S21 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 5. Top: 81% yield, 5a: 5b: 5c: 5d = 18: 14: 41: 27. Bottom: 0% yield. 5a: -120.3 ppm; 5b: -118.4 ppm; 5c: -186.8 ppm; 5d: -189.5 ppm.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

15

Figure S22 19F-NMR spectra of products from fluorination reaction of 5 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: 62% yield. 5a:5b = 51:49 Bottom: 0% yield. 5a: -120.3 ppm; 5b: -118.4 ppm.

Figure S23 19F-NMR spectra of products from fluorination reaction of 5 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst, 95% yield. 5a:5b: 5c: 5d = 35:28:21:15. 5a: -120.3 ppm; 5b: -118.4 ppm; 5c: -186.28 ppm; 5d: -188.94 ppm.

Nano Res.

| www.editorialmanager.com/nare/default.asp

16

S7.9 2-Fluorodiphenylmethane (6a), 4-Fluorodiphenylmethane (6b) and multi-fluorinated products (6c)

Figure S24 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 6. Top: 100% yield, 6a: 6b = 44: 56. Bottom: 0% yield. 6a:-118.6 ppm; 6b: -118.2 ppm.

Figure S25 19F-NMR spectra of products from fluorination reaction of 6 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: 68% yield, 6a:6b:6c = 42:42:16. Bottom; 0% yield. 6a:-118.6 ppm; 6b: -118.2 ppm; 6c: -117.96 ppm; -118.15 ppm; -118.58 ppm; -118.72 ppm.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

17

Figure S26 19F-NMR spectra of products from fluorination reaction of 6 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst, 64% yield. 6a:6b:6c = 32:30:38. 6a:-118.6 ppm; 6b: -118.2 ppm; 6c: -117.96 ppm; -118.15 ppm; -118.58 ppm; -118.72 ppm.

S7.10 4,6-Dichloro-2-(2-fluorophenyl)-5-phenylpyrimidine (7a) and 4,6-dichloro-2-(4-fluorophenyl)-5-phenylpy-rimidine (7b) ( The 19F-NMR chemical shift was reported by previous literature3)

Figure S27 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 7. Top: 7% yield, 7a: 7b = 70: 30. Bottom; 0% yield. 7a:-113.8 ppm; 7b: -109.3 ppm.

Nano Res.

| www.editorialmanager.com/nare/default.asp

18

Figure S28 19F-NMR spectra of products from fluorination reaction of 7 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: 30% yield, 7a:7b = 57:43. Bottom: 0% yield. 7a:-113.8 ppm; 7b: -109.3 ppm.

Figure S29 19F-NMR spectra of products from fluorination reaction of 7 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst, 59% yield . 7a:7b = 53:47. 7a:-113.8 ppm; 7b: -109.3 ppm.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

19

S7.11 F-Butyl ciprofibrate (8a) ( The 19F-NMR chemical shift was reported by previous literature3)

Figure S30 19F-NMR spectra of products from reaction between F-Pd-MOL-phenCl or Selectfluor and 8. Top: 52% yield Bottom: 0% yield. 8a: -131.2 ppm

Figure S31 19F-NMR spectra of products from fluorination reaction of 8 using Pd-MOL-phenCl as hetergeneous catalyst or without catalyst. Top: 34% yield Bottom: 0% yield. 8a: -131.2 ppm

Nano Res.

| www.editorialmanager.com/nare/default.asp

20

Figure S32 19F-NMR spectra of products from fluorination reaction of 8 using [PdII(TPY-OMe)(phenCl)]2+ as homogeneous catalyst, 21% yield. 8a: -131.2 ppm

S7.12 Reaction using the heterogeneous catalyst.

S7.12.1 Catalysis using the MOL

MOL (5 mg, 2 μmol, 2 mol% ) and 2-chloro-1,10-phenanthroline (1 mg, 4 μmol, 4mol%) were added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (1 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 2-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR (0% yield).

S7.12.2 Pd-MOL-phenCl without activation by HBF4·OEt

S7.12.2.1 Preparation of Pd-MOL-phenCl without activation by HBF4·OEt The MOLs (5mg, 2 μmol) were metalated with Pd(OAc)2 (1.05 equiv relative to TPY) overnight in MeCN and then washed with MeCN three times, affording an orange Pd-MOL. Then addition of 2-Chloro-1,10-phenanthroline (1 mg, 4 μmol, 4mol%) afforded Pd-MOL-phenCl, after stirring vigorously for 10 mins and being washed with acetonitrile three time. S7.12.2.2 Fluorination of 4-cyanobiphenyl

Pd-MOL (5 mg, 2 μmol, 2 mol% ) (without activation of HBF4·OEt) and 2-chloro-1,10-phenanthroline (1 mg, 4 μmol, 4mol%) were added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (1 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 4-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

21

S7.12.3 Cross-over experiment.

Pd-MOL-phenCl (5 mg, 2 μmol, 2 mol%) was added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, we seperated the Pd-MOL-phenCl via contrifugation and added 2-phenylpyridine 7 (15.5 mg, 14.3 μL, 0.1 mmol, 1 equiv.) in the solution with Selectflour (70 mg, 0.2 mmol, 2 equiv.). After stirring for 36 hours at 50oC, 2-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR. We only obtained the products of 4-cyanobiphenyl 1 (60% yield). After the fisrt catalytic run, we reused the seperated Pd-MOL-phenCl for the fluorination of 2-phenylpyridine 4 following similar procedure, and we calculated the yield of 2-phenylpyridine 4 by 19F-NMR spectrum (71% yield). 4-flourobenzotrifluoride or 2-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard.

Figure S33 19F-NMR spectra of products from cross-over experiment. (a) Spectrum of products 1a and 1b, yeild: 60%. (b) Spectrum of products 4a and 4b, yeild: 71%.

S7.12.4 The control experiments of different co-ligands in the heterogeneous catalysts

S7.12.4.1 2,2-Bispyridine replacing the 2-chloro-1,10-phenanthroline

Pd-MOL (5 mg, 2 μmol, 2 mol%) and 2-methyl-1,10-phenanthroline (phen CH3) (078 mg, 4 μmol, 4mol%) were added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 2-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR (0% yield).

Nano Res.

| www.editorialmanager.com/nare/default.asp

22

S7.12.4.2 1,10-phenanthroline replacing the 2-chloro-1,10-phenanthroline

Pd-MOL (5 mg, 2 μmol, 2 mol% ) and phenanthroline (phen) (0.72 mg, 4 μmol, 4mol%) were added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 2-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR (7% yield). S7.12.4.3 2,2-Bispyridine replacing the 2-chloro-1,10-phenanthroline

Pd-MOL (5 mg, 2 μmol, 2 mol% ) and 2,2'-bipyridine (bpy) (0.62 mg, 4 μmol, 4mol%) were added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 2-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR (0% yield). S7.12.4.4 Without co-ligand

Pd-MOL (5 mg, 2 μmol, 2 mol%) was added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 2-flourobenzotrifluoride (13 mg, 10 μL, 80 μmol, 0.8 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR (0% yield).

Table S8 Summerization of control experiments of heterogenous catalyst

Y phenCl phenCH3 phen bpy nothing Yield % 90 19 7 0 0

S7.12.5 Reuse test

Pd-MOL-phenCl (5 mg, 2 μmol, 2 mol% ) was added to a 25 mL round bottom flask containing a solution of Selectflour (70 mg, 0.2 mmol, 2 equiv.) and 4-cyanobiphenyl 1 (18 mg, 0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, 4-flourobenzotrifluoride (6.5 mg, 5 μL, 40 μmol, 0.4 equiv.) was added as an internal standard. The yield was determined by integrations in 19F-NMR. The collected Pd-MOL-phenCl was then used in subsequent reaction runs. At each round, we added 0.7 mg of phenCl in the reaction solution, the yield was determined by integrations in 19F-NMR. After each recycle reaction, the amount of leaking Pd in solution was analyzed by ICP-MS.

Figure S34 Recycle test of Pd-MOL-phenCl as heterogeneous catalyst.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

23

Section S8 Extended x-ray absorption fine structure (EXAFS) of Pd-MOL-X and F-Pd-MOL-X

Table S9 Scattering Paths, Path lengths, and Mean-Square Disorder of the Path Disatance for the EXAFS Fittings

Sample Scattering path R (Å) σ2 (Å2) Fitted Coordination no. Pd-MOL-phenCl Pd-N 2.04±0.01 0.003±0.003 5.3±1.5

F-Pd-MOL-phenCl Pd-N 2.02±0.01 0.003±0.003 5.3±0.8 Pd-MOL-phen Pd-N 2.02±0.01 0.0025±0.003 5.5±1.3

F-Pd-MOL-phen Pd-N 2.02±0.01 0.0029±0.002 5.4±0.9

Figure S35 EXAFS data and the fitting in R space of (a) Pd-MOL-phenCl, (b) F-Pd-MOL-phenCl, (c) Pd-MOL-phen, and (d) F-Pd-MOL-phen. The red plots display the magnitude of the Fourier transform of sample, showing the surrounding atoms adjacent to Pd atoms. The blue plots display the real component. The data and fittings with k-weighting of 3 are displayed.

Section S9 NMR study of the reactive center in the F-Pd-MOL-phenCl 1H-NMR characterization of active species.

Pd-MOL-phenCl (5 mg, 2 μmol, 2 mol% ) was added to a 25 mL round bottom flask containing a solution of Selectfluor (70 mg,

0.2 mmol, 2 equiv.) and 2-chlor-phenanthroline (21.4 mg, 0.1 mmol, 1 equiv.) in acetonitrile (2 mL, final c=0.05 M). After stirring for 36 hours at 50 oC, we added CD3CN into the solution mixture for 1H-NMR analysis.

Figure S36 1H-NMR spectra of [N-(FO)-phenCl]+ (purple) and phenCl (pink).

Nano Res.

| www.editorialmanager.com/nare/default.asp

24

References [S1] Cao, L.; Lin, Z.; Peng, F.; Wang, W.; Huang, R.; Wang, C.; Yan, J.; Liang, J.; Zhang, Z.; Zhang, T.; Long, L.; Sun, J.; Lin, W., Self-Supporting

Metal–Organic Layers as Single-Site Solid Catalysts. Angew. Chem., Int. Ed. 2016, 55 (16), 4962-4966. [S2] Mazzotti, A. R.; Campbell, M. G.; Tang, P.; Murphy, J. M.; Ritter, T., Palladium(III)-Catalyzed Fluorination of Arylboronic Acid Derivatives. J. Am.

Chem. Soc. 2013, 135 (38), 14012-14015. [S3] Yamamoto, K.; Li, J.; Garber, J. A. O.; Rolfes, J. D.; Boursalian, G. B.; van, G. M.; Neese, F.; Ritter, T.; Yamamoto, K.; Garber, J. A. O.; Rolfes, J.

D.; Boursalian, G. B.; Borghs, J. C.; Ritter, T.; Genicot, C.; Jacq, J., Palladium-catalysed electrophilic aromatic C-H fluorination. Nature 2018, 554 (7693), 511-514.

[S4] Fukaya, H.; Ono, T., DFT-GIAO calculations of 19F NMR chemical shifts for perfluoro compounds. J. Comput. Chem. 2004, 25 (1), 51-60. [S5] Adcock, W., A DFT-GIAO and DFT-NBO study of polar substituent effects on NMR 17O chemical shifts in some rigid polycyclic alkanes. J. Phys.

Org. Chem. 2011, 24 (6), 492-498.