Supporting Information

Supporting Information An In Situ One-Pot Synthetic Approach towards Multivariate Zirconium MOFs Yujia Sun, Lixian Sun, Dawei Feng,* and Hong-Cai Zhou* anie_201602274_sm_miscellaneous_information.pdf

Contents Section S1. Materials and Instrumentation.. S3 Section S2. MOF Synthesis..... S5 Section S3. Powder X-ray Diffraction... S17 Section S4. IR Spectra.. S21 Section S5. N 2 Uptake...S28 Section S6. Thermal Stability Analyses....S33 Section S7. Chemical Stability Measurements.....S35 Section S8. Controllable Incorporation of NiTCPP into UiO-66...S38 Section S9. SEM Images... S40 Section S10. SEM/EDS Analyses.....S43 Section S11. 1 H NMR Spectra...S45 Section S12. Control Experiments...S47 Section S13. Comparison of X UiO-66 and X UiO-66-NH 2...S52 Section S14. Porphyrin UiO-66 Systems with Incorporation of Multiple Functionalities....S54 Section S15. Catalytic Activity Test.....S55 Section S16. Thermodynamics behind Our Strategy.......S59 Section S17. Calculation of the plausible chemical formula..s60 S2

Section S1. Materials and Instrumentation. Methyl 4-formylbenzoate was purchased from Oakwood Products, Inc. Pyrrole, propionic acid, N,N-dimethylformamide (DMF), benzoic acid, acetone, zirconium(iv) chloride, iron(ii) chloride tetrahydrate (FeCl2 4H2O), manganese(ii) chloride tetrahydrate (MnCl2 4H2O), nickel(ii) chloride hexahydrate (NiCl2 6H2O), cobalt(ii) chloride hexahydrate (CoCl2 6H2O), copper(ii) chloride tetrahydrate (CuCl2 4 H2O), and zinc(ii) chloride (ZnCl2, anhydrous) were purchased from Alfa Aesar. Terephthalic acid (BDC), 2-aminoterephthalic acid (NH2-BDC), 2,5-dihydroxyterephthalic acid (DOBDC), 1,2,4,5-benzenetetracarboxylic acid (H4BTeC) were purchased from Sigma-Aldrich. Tetrakis(4-carboxyphenyl)porphyrin (H2TCPP), Tetrakis(4- methylphenyl)porphyrin, [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Mn(III) Chloride (MnTCPPCl), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Fe(III) Chloride (FeTCPPCl), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Zn(II) (ZnTCPP), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Ni(II) (NiTCPP), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Co(II) (CoTCPP), [5,10,15,20- Tetrakis(4-carboxyphenyl)porphyrinato]-Cu(II) (CuTCPP) were synthesized according to the procedure in previous reports with slight modifications. 1 2-Azido terephthalic acid was synthesized according to the procedure in the literature. 2 All commercial chemicals were used without further purification unless otherwise mentioned. Powder X-ray diffraction (PXRD) was carried out with a BRUKER D8-Focus Bragg Brentano X-ray powder diffractometer equipped with a Cu-sealed tube (λ = 1.54178) at 40 kv and 40 ma. Thermogravimetric analysis (TGA) were conducted on S3

a Shimadzu TGA-50 thermogravimetric analyzer from room temperature to 700 C at a ramp rate of 2 C/min in a flowing nitrogen atmosphere. Nuclear magnetic resonance (NMR) spectra were collected on a Mercury 300 spectrometer. The UV-vis absorption spectra were recorded on a Shimadzu UV-2450 spectrophotometer. N2 adsorptiondesorption isotherms were measured by using a Micrometritics ASAP 2420 system at 77 K. Sample was activated by solvent exchange (in several cycles using fresh acetone), followed by degassing at elevated temperature (100 C) for 3 h. Elemental microanalyses (EA) were performed on vario EL cube Elementar. Scanning electron microscope (SEM) was performed on QUANTA 450 FEG and energy dispersive X-ray spectroscopy (EDS) was carried out by X-Max20 with Oxford EDS system equipped with X-ray mapping. S4

Section S2. MOF Synthesis. Synthesis of NiTCPP UiO-66 ZrCl4 (30 mg, 0.129 mmol), BDC (20 mg, 0.120 mmol), NiTCPP (10 mg, 0.012 mmol) and benzoic acid (600 mg, 4.918 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solventexchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of UiO-66 ZrCl4 (30 mg, 0.129 mmol), BDC (20 mg, 0.120 mmol) and benzoic acid (600 mg, 4.918 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, white precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting white powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of NiTCPP UiO-66-NH2 ZrCl4 (30 mg, 0.129 mmol), NH2-BDC (20 mg, 0.110 mmol), NiTCPP (10 mg, 0.012 mmol) and benzoic acid (600 mg, 4.918 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After S5

cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of UiO-66-NH2-S1 ZrCl4 (30 mg, 0.129 mmol), NH2-BDC (20 mg, 0.110 mmol) and benzoic acid (600 mg, 4.918 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, white precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting white powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-NH2 ZrCl4 (30 mg, 0.129 mmol), NH2-BDC (20 mg, 0.110 mmol), FeTCPPCl (10 mg, 0.011 mmol) and benzoic acid (600 mg, 4.918 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, brown precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting brown powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of MnTCPP UiO-66-NH2 ZrCl4 (30 mg, 0.129 mmol), NH2-BDC (30 mg, 0.166 mmol), MnTCPPCl (10 mg, S6

0.011 mmol) and benzoic acid (500 mg, 4.098 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, dark green precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting dark green powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of CuTCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg CuTCPP (0.012 mmol)was used. Synthesis of ZnTCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg H2TCPP (0.013 mmol)was used. Synthesis of CoTCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg CoTCPP (0.012 mmol)was used. Synthesis of FeTCPP UiO-66 ZrCl4 (30 mg, 0.129 mmol), BDC (30 mg, 0.181 mmol), FeTCPPCl (10 mg, 0.011 mmol) and benzoic acid (500 mg, 4.098 mmol) in 2 ml of DMF were ultrasonically S7

dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, brown precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting brown powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of MnTCPP UiO-66 ZrCl4 (30 mg, 0.129 mmol), BDC (50 mg, 0.301 mmol), MnTCPPCl (10 mg, 0.011 mmol) and benzoic acid (500 mg, 4.098 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, dark green precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting dark green powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of CuTCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg CuTCPP (0.012 mmol) was used. Synthesis of ZnTCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg H2TCPP (0.013 mmol) was used. S8

Synthesis of CoTCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of NiTCPP UiO-66-2,5-(OH)2 ZrCl4 (30 mg, 0.129 mmol), DOBDC (60 mg, 0.303 mmol), NiTCPP (10 mg, 0.012 mmol) and benzoic acid (320 mg, 2.623 mmol) in 2 ml of DMF and 1 d H2O were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 105 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg MnTCPPCl (0.011 mmol) was used. Synthesis of CuTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg CuTCPP (0.012 mmol)was used. Synthesis of H2TCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that S9

10 mg H2TCPP (0.013 mmol) was used. Synthesis of ZnTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg ZnTCPP (0.012 mmol)was used. Synthesis of CoTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg CoTCPP (0.012 mmol)was used. Synthesis of NiTCPP UiO-66-2,5-(CH3)2 ZrCl4 (20 mg, 0.086 mmol), 2,5-dimethylterephthalic acid (50 mg, 0.258 mmol), NiTCPP (10 mg, 0.012 mmol) and benzoic acid (250 mg, 2.049 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg MnTCPPCl (0.011 mmol) was used. Synthesis of CuTCPP UiO-66-2,5-(CH3)2 S10

The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg CuTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg H2TCPP (0.013 mmol) was used. Synthesis of ZnTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of CoTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of NiTCPP UiO-66-SO3H ZrCl4 (20 mg, 0.086 mmol), monosodium salt of 2-sulfonyl terephthalic acid (60 mg, 0.224 mmol) and NiTCPP (10 mg, 0.012 mmol) in 0.7 ml of acetic acid and 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, washed with H2O twice to remove salts, and then solventexchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-SO3H The same reaction conditions as synthesis of NiTCPP UiO-66-SO3H, except that 10 S11

mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-SO3H ZrCl4 (30 mg, 0.129 mmol), monosodium salt of 2-sulfonyl terephthalic acid (80 mg, 0.298 mmol) and MnTCPPCl (5 mg, 0.006 mmol) in 0.7 ml of acetic acid and 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, dark green precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, washed with H2O twice to remove salts, and then solventexchanged with acetone three times. The resulting dark green powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of CuTCPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg CuTCPP (0.006 mmol) was used. Synthesis of H2CPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg H2TCPP (0.006 mmol) was used. Synthesis of ZnTCPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg ZnTCPP (0.006 mmol) was used. Synthesis of CoTCPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg CoTCPP (0.006 mmol) was used. S12

Synthesis of NiTCPP UiO-66-2,5-(COOH)2 ZrCl4 (100 mg, 0.429 mmol), H4BTeC (120 mg, 0.472 mmol) and NiTCPP (10 mg, 0.012 mmol) in 0.3 ml of TFA, 0.1 ml of H2O and 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 10 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 5 mg MnTCPPCl (0.006 mmol) was used. Synthesis of CuTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 5 mg CuTCPP (0.006 mmol) was used. Synthesis of H2TCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 5 mg H2TCPP (0.006 mmol) was used. Synthesis of ZnTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except S13

that 5 mg ZnTCPP (0.006 mmol) was used. Synthesis of CoTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of NiTCPP UiO-66-N3 ZrCl4 (20 mg, 0.086 mmol), 2-azido terephthalic acid (40 mg, 0.193 mmol), NiTCPP (10 mg, 0.012 mmol) and benzoic acid (320 mg, 2.623 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg MnTCPPCl (0.011 mmol) was used. Synthesis of CuTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg CuTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66-N3 S14

The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg H2TCPP (0.013 mmol) was used. Synthesis of ZnTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of CoTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of TBPP UiO-66 The same reaction conditions as synthesis of NiTCPP UiO-66-1, except that 10 mg TBPP (0.010 mmol) was used. Synthesis of PP UiO-66 The same reaction conditions as synthesis of NiTCPP UiO-66-1, except that 15 mg protoporphyrin IX (PP) (0.027 mmol) was used. Synthesis of CoTCP UiO-66 ZrCl4 (30 mg, 0.129 mmol), BDC (30 mg, 0.180 mmol), CoTCP (5 mg, 0.004 mmol) and benzoic acid (500 mg, 4.098 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 20 h. After cooling down to room temperature, the precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solventexchanged with acetone three times. The resulting light yellow powder was obtained by centrifugation, and dried in an oven at 80 C. S15

Synthesis of BBA UiO-66 ZrCl4 (30 mg, 0.129 mmol), BDC (20 mg, 0.120 mmol), 4-bromobenzoic acid (BBA, 10 mg, 0.050 mmol) and benzoic acid (500 mg, 4.098 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 20 h. After cooling down to room temperature, the precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting white powder was obtained by centrifugation, and dried in an oven at 80 C. S16

Section S3. Powder X-ray Diffraction. Figure S1. PXRD profiles for X UiO-66 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). Figure S2. PXRD profiles for X UiO-66-NH2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S17

Figure S3. PXRD profiles for X UiO-66-2,5-(OH)2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). Figure S4. PXRD profiles for X UiO-66-2,5-(CH3)2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S18

Figure S5. PXRD profiles for X UiO-66-SO3H (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). Figure S6. PXRD profiles for X UiO-66-2,5-(COOH)2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S19

Figure S7. PXRD profiles for X UiO-66-N3 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S20

Section S4. IR Spectra. Figure S8. IR spectrum of NiTCPP UiO-66. Figure S9. IR spectrum of FeTCPPCl UiO-66. S21

Figure S10. IR spectrum of MnTCPPCl UiO-66. Figure S11. IR spectrum of CuTCPP UiO-66. S22

Figure S12. IR spectrum of H2TCPP UiO-66. Figure S13. IR spectrum of ZnTCPP UiO-66. S23

Figure S14. IR spectrum of CoTCPP UiO-66. Figure S15. IR spectrum of NiTCPP UiO-66-NH2. S24

Figure S16. IR spectrum of NiTCPP UiO-66-2,5-(OH)2. Figure S17. IR spectrum of NiTCPP UiO-66-2,5-(CH3)2. S25

Figure S18. IR spectrum of NiTCPP UiO-66-SO3H. Figure S19. IR spectrum of CuTCPP UiO-66-2,5-(COOH)2. S26

Figure S20. IR spectrum of NiTCPP UiO-66-N3. S27

Section S5. N2 Uptake. Before the N2 uptake experiment, 120 mg samples were activated using the outgas function of the adsorption instrument at 100 C for 3 h prior to gas adsorption/desorption measurement. Figure S21. N2 adsorption/desorption isotherms of UiO-66 and NiTCPP UiO-66 at 77 K, 1 atm. S28

Figure S22. N2 adsorption/desorption isotherms of UiO-66 and NiTCPP UiO-66 at 77 K, 1 atm, presented in semi-logarithmic scale. Figure S23. DFT pore size distribution of UiO-66 using data measured with N2 at 77 K. S29

Figure S24. DFT pore size distribution of NiTCPP UiO-66 using data measured with N2 at 77 K. Figure S25. N2 adsorption/desorption isotherms of UiO-66-NH2 and NiTCPP UiO- 66-NH2 at 77 K, 1 atm. S30

Figure S26. N2 adsorption/desorption isotherms of UiO-66-NH2 and NiTCPP UiO- 66-NH2 at 77 K, 1 atm, presented in semi-logarithmic scale. Figure S27. DFT pore size distribution of UiO-66-NH2 using data measured with N2 at 77 K. S31

Figure S28. DFT pore size distribution of NiTCPP UiO-66-NH2 using data measured with N2 at 77 K. S32

Section S6. Thermal Stability Analyses. 10.0 mg of fresh as-synthesized MOF samples were heated on the TGA-50 (Shimadzu) thermogravimetric analyzer from room temperature to 700 C at a ramp rate of 2 C/min under N2 flow of 25 ml/min. The observed decomposition temperature is around 400 C for NiTCPP UiO-66 and 350 C for NiTCPP UiO-66-NH2, suggesting the excellent thermal stability of MOF samples. Figure S29. Thermogravimetric analysis of NiTCPP UiO-66. S33

Figure S30. Thermogravimetric analysis of NiTCPP UiO-66-NH2. S34

Section S7. Chemical Stability Measurements. NiTCPP UiO-66 and NiTCPP UiO-66-NH2 samples were selected as examples for chemical stability measurements. First, 1 M HCl, 2 M HCl, 6 M HCl, 1 mm NaOH and 10 mm NaOH aqueous solutions were prepared. Then, 100 mg of sample was immersed in 50 ml of each aqueous solution and water for 12 h. After that, all the samples were centrifuged and the solids were washed with water, DMF and acetone three times in turn and dried in the oven. These samples were characterized by powder X-ray diffraction. Then, all the samples were degassed on ASAP 2420 adsorption system at 100 C for 3 h prior to N2 adsorption measurement at 77 K. Figure S31. Powder X-ray diffraction (PXRD) profiles for NiTCPP UiO-66 without treatment of any aqueous solutions and the samples treated with water, 1 M HCl, 2 M HCl, 6 M HCl, and 1 mm NaOH aqueous solutions for 12 h. S35

Figure S32. Powder X-ray diffraction (PXRD) profiles for NiTCPP UiO-66-NH2 without treatment of any aqueous solutions and the samples treated with water, 1 M HCl, 2 M HCl, 6 M HCl, 1 mm NaOH and 10 mm NaOH aqueous solutions for 12 h. Figure S33. N2 adsorption isotherms of NiTCPP UiO-66 at 77 K, 1 atm after treatment with aqueous solutions with different ph. S36

Figure S34. N2 adsorption isotherms of NiTCPP UiO-66-NH2 at 77 K, 1 atm after treatment with aqueous solutions with different ph. Figure S35. The PXRD patterns for PCN-222(Ni) and PPF-5 before and after treatment in the stability test. S37

Section S8. Controllable Incorporation of NiTCPP into UiO- 66. To carry out the experiment, different amount of NiTCPP was used (3 mg, 0.004 mmol; 6 mg, 0.007 mmol; 9 mg, 0.011 mmol; 12 mg, 0.014 mmol; 15 mg, 0.018 mmol; 18 mg, 0.021 mmol). ZrCl4 (30 mg, 0.129 mmol), BDC (20 mg, 0.120 mmol), NiTCPP and benzoic acid (600 mg, 4.918 mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solventexchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Figure S36. Ni to Zr atomic ratio in NiTCPP UiO-66 with different amounts of NiTCPP ligand used in the synthesis. S38

Figure S37. The PXRD patterns for UiO-66 and NiTCPP UiO-66 with different amounts of NiTCPP used in the synthesis. S39

Section S9. SEM Images. Figure S38. Representative SEM images of NiTCPP UiO-66-NH2. S40

Figure S39. Representative SEM image of NiTCPP UiO-66-NH2 single crystal and corresponding EDS-mappings of Ni, Zr, C, N, O from left to right. Figure S40. Representative SEM image of NiTCPP UiO-66. Figure S41. Representative SEM image of NiTCPP UiO-66 single crystal and corresponding EDS-mappings of Ni, Zr, C, N, O from left to right. S41

Figure S42. Representative SEM image of FeTCPPCl UiO-66. Figure S43. Representative SEM image of FeTCPPCl UiO-66-NH2. S42

Section S10. SEM/EDS Analyses. Figure S44. SEM/EDS analysis for NiTCPP UiO-66. Table S1. Atomic ratio in NiTCPP UiO-66 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Ni 0.51 0.13 0.41 0.10 0.57 0.15 Zr 17.03 2.86 13.63 2.23 18.53 3.14 Average Ni: Zr ratio: 0.046: 1 S43

Figure S45. SEM/EDS analysis for NiTCPP UiO-66-NH2. Table S2. Atomic ratio in NiTCPP UiO-66-NH2 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Ni 0.08 0.02 0.09 0.02 0.47 0.12 Zr 2.72 0.38 2.61 0.37 15.38 2.53 Average Ni: Zr ratio: 0.051: 1 S44

Section S11. 1 H NMR Spectra. Approximately 15 mg of dried MOF sample was digested in 5 ml 16% HF solution. The tube was them immersed in boiling water to evaporate HF. The dried product was dissolved in DMSO-d6 for 1 H NMR test. Figure S46. Solution 1 H NMR spectrum used to determine the ratio of (a) NiTCPP and (b) BDC in NiTCPP UiO-66. 1 H NMR of digested NiTCPP UiO-66 (300 MHz, DMSO-d6). BDC δ: 8.00 (s, 4H). NiTCPP δ: 8.13 (d, J = 7.8 Hz, 8H), 8.30 (d, J = 8.2 Hz, 8H), 8.75 (s, 8H). Molar ratio based on integration of the peaks: NiTCPP: BDC = 0.075: 1. S45

Figure S47. Solution 1 H NMR spectrum used to determine the ratio of (a) NiTCPP and (b) NH2-BDC in NiTCPP UiO-66-NH2. 1 H NMR of digested NiTCPP UiO-66-NH2 (300 MHz, DMSO-d6). NH2-BDC δ: 6.99 (d, J = 8.3 Hz, 1H), 7.36 (s, 1H), 7.75 (d, J = 8.3 Hz, 1H). NiTCPP δ: 8.13 (d, J = 8.2 Hz, 8H), 8.30 (d, J = 8.0 Hz, 8H), 8.75 (s, 8H). Molar ratio based on integration of the peaks: NiTCPP: NH2-BDC = 0.071: 1. S46

Section S12. Control Experiments Figure S48. The product obtained after stirring UiO-66 and NiTCPP in DMF for 12 h (a) at room temperature; (b) at 85 C. (c) NiTCPP UiO-66. (d) The PXRD patterns of UiO-66 and products obtained after stirring UiO-66 and NiTCPP in DMF for 12 h at different temperatures. S47

Figure S49. Solution 1 H NMR spectrum of the product dissolved in DMSO-d6. The product was obtained after stirring UiO-66 and NiTCPP in DMF for 12 h at room temperature or at 85 C. No peaks of NiTCPP were observed. Figure S50. (i) Tetrahedral pore in UiO-66 with a diameter of 7.5 Å. (ii) Octahedral pore in UiO-66 with a diameter of 12 Å. (iii) NiTCPP. S48

Figure S51. (a) Photographs of (i) NiTCPP UiO-66, (ii) TBPP UiO-66, and (iii) PP UiO-66 samples. (b) The PXRD patterns for these samples. S49

Figure S52. IR spectrum of TBPP UiO-66. Figure S53. Photographs of (i) BBA UiO-66 and (ii) CoTCP UiO-66. S50

Figure S54. The PXRD patterns for CoTCP UiO-66 and BBA UiO-66. Table S3. Atomic ratio in BBA UiO-66 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Br 0.56 0.13 0.18 0.04 0.13 0.03 Zr 30.61 6.11 30.08 5.94 29.38 5.75 Average Br: Zr ratio: 0.011: 1 Table S4. Atomic ratio in CoTCP UiO-66 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Co 0.55 0.18 0.32 0.10 0.30 0.09 Zr 34.25 7.11 33.45 6.86 32.01 6.52 Average Co: Zr ratio: 0.018: 1 Since the size of CoTCP ligand is larger than TCPP ligand, the amount of CoTCP used in the synthesis was one third of NiTCPP in order to guarantee the formation of phasepure products. S51

Section S13. Comparison of X UiO-66 and X UiO-66-NH2. Figure S55. X UiO-66 samples in DMF after shaking to make the color better observed. From left to right were NiTCPP UiO-66, FeTCPPCl UiO-66, MnTCPPCl UiO-66, CuTCPP UiO-66, H2TCPP UiO-66 and ZnTCPP UiO-66. Figure S56. X UiO-66 samples in DMF with final powders attached on the bottom. From left to right were NiTCPP UiO-66, FeTCPPCl UiO-66, MnTCPPCl UiO-66, CuTCPP UiO-66, H2TCPP UiO-66 and ZnTCPP UiO-66. S52

Figure S57. X UiO-66-NH2 samples in DMF after shaking to make the color better observed. From left to right were NiTCPP UiO-66-NH2, FeTCPPCl UiO-66-NH2, MnTCPPCl UiO-66-NH2, CuTCPP UiO-66-NH2, H2TCPP UiO-66-NH2 and ZnTCPP UiO-66-NH2. Figure S58. X UiO-66-NH2 samples in DMF with final powders attached on the bottom. From left to right were NiTCPP UiO-66-NH2, FeTCPPCl UiO-66-NH2, MnTCPPCl UiO-66-NH2, CuTCPP UiO-66-NH2, H2TCPP UiO-66-NH2 and ZnTCPP UiO-66-NH2. S53

Section S14. Porphyrin UiO-66 Systems with Incorporation of Multiple Functionalities. Figure S59. Photographs of (a) X UiO-66, (b) X UiO-66-NH2, (c) X UiO-66-2,5- (OH)2, (d) X UiO-66-2,5-(CH3)2, (e) X UiO-66-SO3H, (f) X UiO-66-2,5-(COOH)2, and (g) X UiO-66-N3 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP from left to right). S54

Section S15. Catalytic Activity Test. In order to show the preservation of the functionality of TCPP species after applying our strategy, we took FeTCPPCl UiO-66 and FeTCPPCl UiO-66-NH2 as examples for the oxidation reaction of 2,2 -azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) in the presence of H2O2 to test the catalytic activity of these MOFs. First, 50 mm ABTS, 10 mm H2O2, and 1g/L MOF solution were prepared. To carry out the experiment, 200 μl ABTS, 80 μl MOF solution, 250 μl H2O2 and 2.47 ml deionized water were added into a Pyrex vial. The addition of FeTCPPCl UiO-66 or FeTCPPCl UiO-66-NH2 and H2O2 to the substrate solution led to the appearance of green color and gave a maximum absorbance at 418 nm, which originated from the formation of oxidized ABTS product (Scheme 1). The increased intensity of the maximum absorbance (Figure S52 and S54) as well as the color change over time (Figure S53, S55 and S57) demonstrated the biomimetic catalytic activity of FeTCPP UiO-66 and FeTCPP UiO-66-NH2 compared to UiO-66. Scheme 1. Reaction catalyzed by FeTCPPCl UiO-66 Figure S60. UV-Vis absorbance changes over time for oxidation reaction of ABTS catalyzed by FeTCPPCl UiO-66. S55

Figure S61. From left to right were the color changes of solution using FeTCPPCl UiO-66 as the catalyst after 1 min, 3 min, 5 min, 7 min, 10 min, 15 min and 20 min. Figure S62. UV-Vis absorbance changes over time for oxidation reaction of ABTS catalyzed by FeTCPPCl UiO-66-NH2. S56

Figure S63. From left to right were the color changes of solution using FeTCPPCl UiO-66-NH2 as the catalyst after 1 min, 3 min, 5 min, 7 min, 10 min, 15 min and 20 min. Figure S64. UV-Vis absorbance after 20 min when using UiO-66. S57

Figure S65. From left to right were the photographs of the solutions after 20 min when using FeTCPPCl UiO-66, FeTCPPCl UiO-66-NH2 and UiO-66, respectively. S58

Section S16. Thermodynamics behind Our Strategy. Figure S66. (a) Equilibrium in formation of the MOF. (b) Expression of Gibbs free energy of the reaction. S59

Section S17. Calculation of the plausible chemical formula. In order to further understand the defect-related problems in our TCPP UiO-66 system, we choose NiTCPP UiO-66 as an example to figure out the plausible chemical formula of the material. According to TGA data (Figure S29), 64.3% of the weight was lost after TGA test for NiTCPP UiO-66. First, we calculate the total amount of Zr and Ni in the material according to TGA data, given that the products remained after TGA analysis were ZrO2 and NiO. Then, we calculate the ratio of Zr to Ni as well as NiTCPP to BDC from EDS data (Table S1) and 1 H NMR data (Figure S46), respectively. After combining all of these results, the preliminary chemical formula of the material can be written as Zr6O4(OH)4(BDC)3.73(NiTCPP)0.28. In order to keep the charge balance, additional hydroxide anions are added. The presence of hydroxide anions to achieve the charge balance in UiO-66 containing defects has been reported by Yaghi group. 3 Finally, the plausible chemical formula of the material can be written as Zr6O4(OH)8(BDC)3.73(NiTCPP)0.28. (C: 32.6%, H: 1.9%, N: 1.0% were calculated from the chemical formula while C: 32.6%, H: 2.0%, N: 1.2% were obtained from the elemental analysis.) Reference (1) Feng, D.; Gu, Z.-Y.; Li, J.-R.; Jiang, H.-L.; Wei, Z.; Zhou, H.-C. Angew. Chem. Int. Ed. 2012, 51, 10307. (2) Kim, M.; Cahill, J. F.; Su, Y.; Prather, K. A.; Cohen, S. M. Chem. Sci. 2012, 3, 126. (3) Trickett, C. A.; Gagnon, K. J.; Lee, S.; Gándara, F.; Bürgi, H.-B.; Yaghi, O. M. Angew. Chem. Int. Ed. 2015, 54, 11162. S60