Deciphering the Spatial Arrangement of Metals and Correlation to. Reactivity in Multivariate Metal-Organic Frameworks

Transcription

1 Deciphering the Spatial Arrangement of Metals and Correlation to Reactivity in Multivariate Metal-Organic Frameworks Qi Liu, Hengjiang Cong, Hexiang Deng *,, Key Laboratory of Biomedical Polymers-Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan , China. The Institute for Advanced Studies, Wuhan University, Wuhan , China. Table of Contents Section S1 Structure design S2 Section S2 Chemicals and characterization S3 Section S3 Syntheses of MOFs, PXRD patterns of S3-S18 as-synthesized crystals Section S4 Single-Crystal X-ray Crystallography S19-S40 Section S5 Activation Procedures S41-S43 Section S6 Thermogravimetric Analysis S44-S45 Section S7 Infrared (IR) spectra of MOFs S46-S47 Section S8 UV-vis spectra of linkers S48 Section S9 N 2 adsorptions analysis S49-S53 Section S10 Photo-oxidation reactions S54-S67 Section S11 X-ray adsorption spectra of MOFs S68-S83 Section S12 Electron Paramagnetic Resonance (EPR) of MOFs S84 Section S13 57 Fe Mössbauer spectroscopy of MOFs S85 Section S14 Ultraviolet-visible diffuse reflectance spectra S86-S94 (UV-vis DRS) of MOFs Section S15 VB-XPS spectra of MOFs S95-S98 References S99-S100 S1

2 Section S1. Structure design Figure S1. (A, C) Crystal structure of (Mg 3 O) 2 (TCPP-Co) 3. Pore size is described by the length of the diagonal and the distance between the two opposite edges in the regular hexagonal cross section. (B) stp topology from the structure. (D) The tiling of the stp topology representing the subdivisions of space. Atom colors: Mg, azure; carbon, grey; nitrogen, blue; oxygen, red. Hydrogen atoms are omitted for clarity. We aimed to construct structures with variation of metals and explore the influence of metals on property. According to previous reports, the majority of SBUs could only correspond to one special metal (S1). However, many kinds of metals could form trigonal prism. It consists of three octahedrons, and each metal is coordinated by four bridging carboxylate groups, a central bridging O 2- and an oxygen atom from terminal water (S2). This kind of SBU could be a good candidate for introduction of metals. In other hand, porphyrin linker can be chelated with varieties of metals in the center. (S3). Thus, the structure contains trigonal prism as SBU and porphyrin as linker could be a perfect model for research of influence of metals on properties with topology maintained. According to the RCSR database (S4), the combination of this kind trigonal prism SBU acting as a 6-connected trigonal-prism-like point and porphyrin linker as a 4-connected square-like point results in a stp topology (S5) (Fig. S1). We note that one MOF with this topology based on Fe 3 O SBU and porphyrin linker, (Fe 3 O) 2 (TCPP-M) 3, has been reported as PCN-600, and the structure was revealed using the unit cell obtained from PXRD refinement (5b). In this study, crystals suitable for single crystal X-ray diffraction were obtained using a different synthetic condition. This allows for the identification of the accurate atomic structure of (Fe 3 O) 2 (TCPP-M) 3 (Section S4). S2

3 Section S2. Chemicals and characterization N,N-dimethylformamide (DMF), cobalt (II) chloride hexahydrate (CoCl 2 6H 2 O), manganese (II) chloride tetrahydrate (MnCl 2 4H 2 O), magnesium(ii) nitrate hexahydrate (Mg(NO 3 ) 2 6H 2 O), nickel (II) nitrate hexahydrate (Ni(NO 3 ) 2 6H 2 O), cobalt (II) nitrate hexahydrate (Co(NO 3 ) 2 6H 2 O), ion (III) chloride hexahydrate (FeCl 3 6H 2 O), acetic acid (HAc), trifluoroacetic acid (TFA) were purchased from China National Medicines Corporation LTD. All chemicals were used without further purifications. All TCPP-M (M=H 2, Mg, Co, Ni, Cu, Zn) were synthesized based on previous reports (S6). SEM measurements were performed on a Merlin Compact FE-SEM, Zeiss. And ICP measurements were performed on a THERMO Intrepid XSP Radial ICP-AES instrument. Section S3. Syntheses of MOFs, PXRD patterns of as-synthesized crystals METHODS: PXRD data was recorded on a Rigaku Smartlab 9KW diffractometer operated at 45 kv, 200 ma for Cu Kα (λ = Å) with a scan speed of 1 º/min and a step size of 0.01º in 2θ at ambient temperature and pressure. Simulated PXRD patterns were calculated using software Mecury 3.0 from the single crystal data. S3

4 Synthesis of (Mg 3 O) 2 (TCPP-H 2 ) 3 Mg(NO 3 ) 2 6H 2 O (5.0mg), TCPP-H 2 (4.2mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mg 3 O) 2 (TCPP-Mg) 3 Mg(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Mg (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mg 3 O) 2 (TCPP-Co) 3 Mg(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Co (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Elemental analysis, C, 49.22; N, 6.21; H, 3.56 %. Synthesis of (Mg 3 O) 2 (TCPP-Ni) 3 Mg(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Ni (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mg 3 O) 2 (TCPP-Cu) 3 Mg(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Cu (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mg 3 O) 2 (TCPP-Zn) 3 Mg(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Zn (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. S4

5 Figure S2. Comparisons of the experimental PXRD pattern of as-synthesized (Mg 3 O) 2 (TCPP- M) 3 with the simulated (Mg 3 O) 2 (TCPP-Co) 3 diffraction pattern. S5

6 Synthesis of (Mn 3 O) 2 (TCPP-H 2 ) 3 MnCl 2 4H 2 O (5.0mg), TCPP-H 2 (4.3mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mn 3 O) 2 (TCPP-Mg) 3 MnCl 2 4H 2 O (5.0mg), TCPP-Mg (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mn 3 O) 2 (TCPP-Co) 3 MnCl 2 4H 2 O (5.0mg), TCPP-Co (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Elemental analysis, C, 57.41; N, 7.75; H, 4.71 %. Synthesis of (Mn 3 O) 2 (TCPP-Ni) 3 MnCl 2 4H 2 O (5.0mg), TCPP-Ni (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mn 3 O) 2 (TCPP-Cu) 3 MnCl 2 4H 2 O (5.0mg), TCPP-Cu (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Mn 3 O) 2 (TCPP-Zn) 3 MnCl 2 4H 2 O (5.0mg), TCPP-Zn (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. S6

7 Figure S3. Comparisons of the experimental PXRD pattern of as-synthesized (Mn 3 O) 2 (TCPP- M) 3 with the simulated (Mn 3 O) 2 (TCPP-Co) 3 diffraction pattern. S7

8 Synthesis of (Co 3 O) 2 (TCPP-H 2 ) 3 CoCl 2 4H 2 O (5.0mg), TCPP-H 2 (4.3mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 36h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Co 3 O) 2 (TCPP-Mg) 3 CoCl 2 4H 2 O (5.0mg), TCPP-Mg (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 36h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Co 3 O) 2 (TCPP-Co) 3 CoCl 2 4H 2 O (5.0mg), TCPP-Co (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 36h. After cooling down to room temperature, dark rod shaped crystals were yielded. Elemental analysis, C, 51.40; N, 8.21; H, 3.89 %. Synthesis of (Co 3 O) 2 (TCPP-Ni) 3 CoCl 2 4H 2 O (5.0mg), TCPP-Ni (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 36h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Co 3 O) 2 (TCPP-Cu) 3 CoCl 2 4H 2 O (5.0mg), TCPP-Cu (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 36h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Co 3 O) 2 (TCPP-Zn) 3 CoCl 2 4H 2 O (5.0mg), TCPP-Zn (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 36h. After cooling down to room temperature, dark rod shaped crystals were yielded. S8

9 Figure S4. Comparisons of the experimental PXRD pattern of as-synthesized (Co 3 O) 2 (TCPP-M) 3 with the simulated (Co 3 O) 2 (TCPP-Co) 3 diffraction pattern. S9

10 Synthesis of (Ni 3 O) 2 (TCPP-H 2 ) 3 Ni(NO 3 ) 2 6H 2 O (5.0mg), TCPP-H 2 (4.4mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Ni 3 O) 2 (TCPP-Mg) 3 Ni(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Mg (5.0mg) Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Ni 3 O) 2 (TCPP-Co) 3 Ni(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Co (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Elemental analysis, C, 49.71; N, 6.65; H, 4.29 %. Synthesis of (Ni 3 O) 2 (TCPP-Ni) 3 Ni(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Ni (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Ni 3 O) 2 (TCPP-Cu) 3 Ni(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Cu (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Ni 3 O) 2 (TCPP-Zn) 3 Ni(NO 3 ) 2 6H 2 O (5.0mg), TCPP-Zn (5.0mg), Trifluoroacetic acid (20μL), Acetic acid (110μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. S10

11 Figure S5. Comparisons of the experimental PXRD pattern of as-synthesized (Ni 3 O) 2 (TCPP-M) 3 with the simulated (Ni 3 O) 2 (TCPP-Co) 3 diffraction pattern. S11

12 Synthesis of (Fe 3 O) 2 (TCPP-Co) 3 FeCl 3 6H 2 O (5.0mg), TCPP-Co (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Elemental analysis, C, 52.08; N, 5.16; H, 4.71 %. Synthesis of (Fe 3 O) 2 (TCPP-Ni) 3 FeCl 3 6H 2 O (5.0mg), TCPP-Ni (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Fe 3 O) 2 (TCPP-Zn) 3 FeCl 3 6H 2 O (5.0mg), TCPP-Zn (5.0mg), Trifluoroacetic acid (75μL) in 2mL of DMF were ultrasonically dissolved in a 4 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Figure S6. Comparisons of the experimental PXRD pattern of as-synthesized (Fe 3 O) 2 (TCPP-M) 3 with the simulated (Fe 3 O) 2 (TCPP-Co) 3 diffraction pattern. S12

13 Synthesis of (Ni 2.46 Fe 0.54 O) 2 (TCPP-Co) 3 FeCl 3 6H 2 O (8.3mg), Ni(NO 3 ) 2 6H 2 O (16.7mg), TCPP-Co (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 FeCl 3 6H 2 O (12.5mg), Ni(NO 3 ) 2 6H 2 O (12.5mg), TCPP-Co (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3 FeCl 3 6H 2 O (18.7mg), Ni(NO 3 ) 2 6H 2 O (4.7mg), TCPP-Co (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Synthesis of (Ni 1.29 Fe 1.71 O) 2 (TCPP-Co) 3 FeCl 3 6H 2 O (21.5mg mg), Ni(NO 3 ) 2 6H 2 O (3.5mg), TCPP-Co (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 12h. After cooling down to room temperature, dark rod shaped crystals were yielded. Figure S7. Comparisons of the experimental PXRD patterns of as-synthesized (Ni x Fe 3- xo) 2 (TCPP-Co) 3 with the simulated diffraction pattern. S13

14 Table S1. Summary of synthesis of MTV-MOF (Ni x Fe 3-x O) 2 (TCPP-Co) 3 series, their added stoichiometric SBU-metal ratio and the ratio found in their crystals. Compound Ni mmol/10ml Fe mmol/10ml Ni : Fe stoichiometric Ratio Ni : Fe Ratio in crystal product (Ni 2.46 Fe 0.54 O) 2 (TCPP-Co) :1 4.6:1 (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) :5 2.2:1 (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) :7 1:1 (Ni 1.29 Fe 1.71 O) 2 (TCPP-Co) :8 0.75:1 S14

15 Synthesis of (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 FeCl 3 6H 2 O (8.3mg), MnCl 2 4H 2 O (16.7mg), TCPP-Ni (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Figure S8. Comparison of the experimental PXRD patterns of as-synthesized (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 with the simulated diffraction pattern. Synthesis of (Mn 2.52 Mg 0.48 O) 2 (TCPP-Ni) 3 Mg(NO 3 ) 2 6H 2 O (12.5mg), MnCl 2 4H 2 O (12.5mg), TCPP-Ni (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Figure S9. Comparison of the experimental PXRD patterns of as-synthesized (Mn 2.52 Mg 0.48 O) 2 (TCPP-Ni) 3 with the simulated diffraction pattern. S15

16 Synthesis of (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 CoCl 2 4H 2 O (20.0mg), MnCl 2 4H 2 O (5.0mg), TCPP-Ni (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Figure S10. Comparison of the experimental PXRD patterns of as-synthesized (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 with the simulated diffraction pattern. Synthesis of (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 Ni(NO 3 ) 2 6H 2 O (8.3mg), MnCl 2 4H 2 O (16.7mg), TCPP-Ni (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Elemental analysis, C, 50.05; N, 7.42; H, 3.97 %. Figure S11. Comparison of the experimental PXRD patterns of as-synthesized (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 with the simulated diffraction pattern. S16

17 Table S2. Summary of synthesis of MTV-MOF (Mn x M 3-x O) 2 (TCPP-Ni) 3 series, their added stoichiometric SBU-metal ratio and the ratio found in their crystals. Compound Mn mmol/10ml M mmol/10ml Mn : M stoichiometric Ratio Mn : M Ratio in crystal product (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) :3 0.94:1 (Mn 2.52 Mg 0.48 O) 2 (TCPP-Ni) :5 5.3:1 (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) :7 1.9:1 (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) :3 1.4:1 S17

18 Synthesis of (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3 Ni(NO 3 ) 2 6H 2 O (12.5 mg), Co(NO 3 ) 2 6H 2 O (12.5 mg), TCPP-Co (25.0mg), Trifluoroacetic acid (375μL) in 10mL of DMF were ultrasonically dissolved in a 20 ml Pyrex vial. The mixture was heated in a 150 C oven for 24h. After cooling down to room temperature, dark rod shaped crystals were yielded. Figure S12. Comparison of the experimental PXRD patterns of as-synthesized (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3 with the simulated diffraction pattern. Table S3. Summary of synthesis of MTV-MOF (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3, its added stoichiometric SBU-metal ratio and the ratio found in its crystals. Compound Ni mmol/10ml Co mmol/10ml Ni : Co stoichiometric Ratio Ni : Co Ratio in crystal product (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) :1 2.6:1 The sharp PXRD peaks of MTV-MOFs show their homogeneity in phase. Based on the elemental analysis, counter-anion OH - and cation dimethylammonium [(CH 3 ) 2 NH 2 ] + were used to balance the charge for the formula of each MOF. In general, the formula of these frameworks can be described as (metal oxide cluster) 2 (TCPP) 3 according to their single crystal structure. Thus the metal cluster center shall have a total charge of 6+. When divalent metals are involved, the formula is [M(II) 3 O(H 2 O) 3 (OH) 2 ] 2 (TCPP) 3, while trivalent metals are involved, the formula is [M(III) 3 O(H 2 O) 3 (CH 3 ) 2 NH 2 )] 2 (TCPP) 3. In the case of MTV-MOFs with both trivalent and divalent metals, the formula is {[M(II) 3- xm(iii) x O(H 2 O) 3 (OH) 2x/3 [(CH 3 ) 2 NH 2 ] (3-x)/3 } 2 (TCPP) 3. Different number of water molecules is added to be consistent with the elemental analysis for each of the MOF. S18

19 Section S4. Single-Crystal X-ray Crystallography All MOFs are large enough for single crystal X-ray analysis. 6 MOFs with different single component SBUs, (Mg 3 O) 2 (TCPP-Co) 3, (Co 3 O) 2 (TCPP-Co) 3, (Ni 3 O) 2 (TCPP-Co) 3, (Mn 3 O) 2 (TCPP-Co) 3, (Fe 3 O) 2 (TCPP-Co) 3, (Mg 3 O) 2 (TCPP- H 2 ) 3, and 2 MTV-MOFs (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3, (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3 were measured as representatives. The single crystal intensity data of (Mg 3 O) 2 (TCPP-Co) 3, (Co 3 O) 2 (TCPP-Co) 3, (Ni 3 O) 2 (TCPP-Co) 3, (Mn 3 O) 2 (TCPP-Co) 3, (Fe 3 O) 2 (TCPP-Co) 3 and MTV-MOF (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3, (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3 were collected at 296K on a Bruker SMART APEXII kappa diffractometer equipped with a CCD detector using Cu Kα radiation with λ=1.5418å (45kV, 0.65mA). The single crystal intensity data of (Mg 3 O) 2 (TCPP-H 2 ) 3 was collected on synchrotron beamline 17U1 of Shanghai Synchrotron Radiation Facility (SSRF) with a wavelength of Å. SBU-metal ratios in MTV-MOFs were fixed based on ICP data. S19

20 METHODS: Data were collected on a Bruker SMART APEXII kappa diffractometer equipped with a CCD area detector and operated (45kV, 0.65mA) to generate Cu Kα radiation (λ = Å). The incident X-ray beam was focused and monochromated using Bruker Excalibur Gobel mirror optics. Crystals were all mounted in flame sealed borosilicate capillaries. For all cases frame widths of 0.5º were judged to be appropriate and full hemispheres of data were collected using the Bruker APEX2 (S7) software suite to carry out overlapping φ and ω scans at different detector (2θ) settings. Following data collection, reflections were sampled from all regions of the Ewald sphere to redetermine unit cell parameters for data integration. Data were integrated using Bruker APEX2 V 2.1 software with a narrow frame algorithm and a fractional lower limit of average intensity. All structures were solved by direct methods and refined using the SHELXTL 97 (S8) and OLEX2 (S9) software suite. Final structures were refined anisotropically until full convergence was achieved. Hydrogen atoms were placed in calculated positions and included as riding atoms. To prove the correctness of the atomic positions in the framework, the application of the SQUEEZE (S10) routine has been performed when applicable. All ellipsoids in ORTEP diagrams are displayed at the 50% probability level unless noted otherwise. The single crystal intensity data was collected on synchrotron beamline 17U1 of Shanghai Synchrotron Radiation Facility (SSRF). S20

21 Table S4. Crystal data and structure refinement for (Co 3 O) 2 (TCPP-Co) 3 Formula C 72 Co 4.5 N 6 O H 46 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (7) b (Å) (7) c (Å) (4) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (7) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 34406/ 8884 Index ranges -30<=h<=28, -27<=k<=31, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1555 GOOF on F S21

22 Table S5. Crystal data and structure refinement for (Co 3 O) 2 (TCPP-Co) 3 (squeeze) Formula C 72 Co 4.5 N 6 O 17.5 H 46 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (7) b (Å) (7) c (Å) (4) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (7) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 34406/ 8884 Index ranges -30<=h<=28, -27<=k<=31, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1555 GOOF on F CCDC number S22

23 Table S6. Crystal data and structure refinement for (Ni 3 O) 2 (TCPP-Co) 3 Formula C 72 Co 1.5 Ni 3 N 6 O H 46 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (14) b (Å) (14) c (Å) (9) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (15) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 33245/ 6169 Index ranges -30<=h<=30, -26<=k<=30, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1576 GOOF on F S23

24 Table S7. Crystal data and structure refinement for (Ni 3 O) 2 (TCPP-Co) 3 (squeeze) Formula C 72 Co 1.5 Ni 3 N 6 O 17.5 H 46 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (14) b (Å) (14) c (Å) (9) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (15) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 33245/ 6169 Index ranges -30<=h<=30, -26<=k<=30, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1576 GOOF on F CCDC number S24

25 Table S8. Crystal data and structure refinement for (Fe 3 O) 2 (TCPP-Co) 3 Formula C 72 Co 1.5 Fe 3 N 6 O 18.5 H 46 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (2) b (Å) (2) c (Å) (11) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14393(2) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique / 2113 Index ranges -23<=h<=28, -26<=k<=24, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1553 GOOF on F S25

26 Table S9. Crystal data and structure refinement for (Fe 3 O) 2 (TCPP-Co) 3 (squeeze) Formula C 72 Co 1.5 Fe 3 N 6 O 17.5 H 46 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (2) b (Å) (2) c (Å) (11) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14393(2) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique / 2113 Index ranges -23<=h<=28, -26<=k<=24, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1537 GOOF on F CCDC number S26

27 Table S10. Crystal data and structure refinement for (Mn 3 O) 2 (TCPP-Co) 3 Formula C 72 Co 1.5 Mn 3 N 6 O H 46 Formula weight Temperature 296(2)K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (3) b (Å) (3) c (Å) (2) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (3) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 33641/ 5800 Index ranges -25<=h<=30, -30<=k<=30, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1567 GOOF on F S27

28 Table S11. Crystal data and structure refinement for (Mn 3 O) 2 (TCPP-Co) 3 (squeeze) Formula C 72 Co 1.5 Mn 3 N 6 O 19 H 46 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (3) b (Å) (3) c (Å) (2) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (3) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 33641/ 5800 Index ranges -25<=h<=30, -30<=k<=30, -11<=l<=15 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1567 GOOF on F CCDC number S28

29 Table S12. Crystal data and structure refinement for (Mg 3 O) 2 (TCPP-Co) 3 Formula C 72 Co 1.5 Mg 3 N 6 O H 46 Formula weight Temperature 296(2)K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (2) b (Å) (2) c (Å) (12) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14841(2) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 18487/ 4141 Index ranges -24<=h<=21, -20<=k<=24, -14<=l<=11 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1465 GOOF on F S29

30 Table S13. Crystal data and structure refinement for (Mg 3 O) 2 (TCPP-Co) 3 (squeeze) Formula C 72 Co 1.5 Mg 3 N 6 O 17.5 H 46 Formula weight Temperature 296(2)K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (2) b (Å) (2) c (Å) (12) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14841(2) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 18487/ 4141 Index ranges -24<=h<=21, -20<=k<=24, -14<=l<=11 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1453 GOOF on F CCDC number S30

31 Table S14. Crystal data and structure refinement for (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3 Formula C 72 Co 2.4 N 6 O 17.5 Ni 2.1 H 36 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (3) b (Å) (3) c (Å) (16) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14788(3) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique / 9940 Index ranges -28<=h<=28, -25<=k<=28, -14<=l<=14 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1547 GOOF on F S31

32 Table S15. Crystal data and structure refinement for (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3 (squeeze) Formula C 72 Co 2.4 N 6 O 17.5 Ni 2.1 H 36 Formula weight Temperature Wavelength Crystal system Space group Space group number (2) K Å hexagonal P 6/m m m a (Å) (3) b (Å) (3) c (Å) (16) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14788(3) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique / 9940 Index ranges θ range/deg Completeness to theta = % R(int) <=h<=28, -25<=k<=28, -14<=l<=14 Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1547 GOOF on F CCDC number S32

33 Table S16. Crystal data and structure refinement for (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3 Formula C 72 Co 1.5 Fe 1.5 N 6 O 17.5 Ni 1.5 H 36 Formula weight Temperature 296(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (11) b (Å) (11) c (Å) (7) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (9) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique / 9860 Index ranges -24<=h<=32, -32<=k<=31, -11<=l<=17 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1453 GOOF on F S33

34 Table S17. Crystal data and structure refinement for (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3 (squeeze) Formula C 72 Co 1.5 Fe 1.5 N 6 O 17.5 Ni 1.5 H 36 Formula weight Temperature Wavelength Crystal system Space group Space group number (2) K Å hexagonal P 6/m m m a (Å) (11) b (Å) (11) c (Å) (7) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) (9) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique / 9860 Index ranges θ range/deg Completeness to theta = % R(int) <=h<=32, -32<=k<=31, -11<=l<=17 Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1537 GOOF on F CCDC number S34

35 Table S18. Crystal data and structure refinement for (Mg 3 O) 2 (TCPP-H 2 ) 3 Formula C 72 Mg 3 N 6 O H 39 Formula weight Temperature 293(2) K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (8) b (Å) (8) c (Å) (5) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14830(8) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 46235/ 6951 Index ranges -31<=h<=31, -31<=k<=30, -14<=l<=13 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1383 GOOF on F S35

36 Table S19. Crystal data and structure refinement for (Mg 3 O) 2 (TCPP-H 2 ) 3 (squeeze) Formula C 72 Mg 3 N 6 O 16 H 39 Formula weight Temperature 296(2)K Wavelength Å Crystal system hexagonal Space group P 6/m m m Space group number 191 a (Å) (8) b (Å) (8) c (Å) (5) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 14830(8) Z 2 Density (calculated) g cm -3 Absorption coefficient Reflns collected/ unique 46235/ 6951 Index ranges -31<=h<=31, -31<=k<=30, -14<=l<=13 θ range/deg Completeness to theta = % R(int) Refinement method Full-matrix least-squares on F 2 Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = F(000) 1383 GOOF on F CCDC number S36

37 Figure S13. ORTEP representation (50% probability) of the crystal structures of (Co 3 O) 2 (TCPP- Co) 3. Atom color, C. grey, O, red, N, blue, Co, green. Figure S14. ORTEP representation (50% probability) of the crystal structures of (Ni 3 O) 2 (TCPP- Co) 3. Atom color, C. grey, O, red, N, blue, Co, green, Ni, purple. S37

38 Figure S15. ORTEP representation (50% probability) of the crystal structures of (Fe 3 O) 2 (TCPP- Co) 3. Atom color, C. grey, O, red, N, blue, Co, green, Fe, yellow. Figure S16. ORTEP representation (50% probability) of the crystal structures of (Mn 3 O) 2 (TCPP- Co) 3. Atom color, C. grey, O, red, N, blue, Co, green, Mn, Deep Red. S38

39 Figure S17. ORTEP representation (50% probability) of the crystal structures of (Mg 3 O) 2 (TCPP- Co) 3. Atom color, C. grey, O, red, N, blue, Mg, Co, green, Mg, azure. Figure S18. ORTEP representation (50% probability) of the crystal structures of (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3. Atom color, C. grey, O, red, N, blue, Co, green, Ni/Co, purple. S39

40 Figure S19. ORTEP representation (50% probability) of the crystal structures of (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3. Atom color, C. grey, O, red, N, blue, Co, green, Ni/Fe, purple. Figure S20. ORTEP representation (50% probability) of the crystal structures of (Mg 3 O) 2 (TCPP- H 2 ) 3. Atom color, C. grey, O, red, N, blue, Mg, azure. S40

41 Section S5. Activation Procedures METHODS: The activation procedures were performed under supercritical CO 2. Before the supercritical CO 2 activation, the as-synthesized samples were immersed in dry DMF for 3 days, during which the activation solvent was decanted and freshly replenished three times. After that, the resulting DMF-exchanged samples were transferred to a 20 ml pyrex vial and refluxed with DMF for 24h using a Soxhlet extractor. Then, the sample was evacuated with supercritical CO 2. For this step, the DMF-containing sample was placed in the chamber and DMF was completely exchanged with liquid CO 2. After this exchange, the chamber containing the sample and liquid CO 2 was heated up around 40 C and held constant at the supercritical condition (typically 1300 psi) for 1 h. The CO 2 was slowly vented (ca. 16 h) from the chamber at around 38 C, yielding porous material. S41

42 Figure S21. Comparisons of the experimental PXRD pattern of activated MOF (Ni 3 O) 2 (TCPP- Co) 3 with the simulated diffraction pattern. Figure S22. Comparisons of the experimental PXRD pattern of activated MOF (Fe 3 O) 2 (TCPP- Co) 3 with the simulated diffraction pattern. S42

43 Figure S23. Comparisons of the experimental PXRD pattern of activated MOF (Ni 3 O) 2 (TCPP- Cu) 3 with the simulated diffraction pattern. Figure S24. Comparisons of the experimental PXRD pattern of activated MOF (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 with the simulated diffraction pattern. S43

44 Section S6. Thermogravimetric (TG) Analysis METHODS: All TG analyses were performed on a TA Instruments Q-500 series thermal gravimetric analyzer with samples held in platinum pans in a continuous air flow atmosphere. Samples were heated at a constant rate of 10 ºC/min during all TGA experiments. Figure S25. TGA trace of activated (Ni 3 O) 2 (TCPP-Mg) 3. Figure S26. TGA trace of activated (Ni 3 O) 2 (TCPP-Co) 3. S44

45 Figure S27. TGA trace of activated (Ni 3 O) 2 (TCPP-Ni) 3. Figure S28. TGA trace of activated (Ni 3 O) 2 (TCPP-Cu) 3. S45

46 Section S7. Infrared (IR) spectra of MOFs METHODS: All IR spectra were recorded on a Nicolet NEXUS670 IR spectroscopy and samples were tableted and KBr was utilized as background. Figure S29. IR spectra of (Mg 3 O) 2 (TCPP-M) 3. Figure S30. IR spectra of (Mn 3 O) 2 (TCPP-M) 3. S46

47 Figure S31. IR spectra of (Co 3 O) 2 (TCPP-M) 3. Figure S32. IR spectra of (Ni 3 O) 2 (TCPP-M) 3. S47

48 Section S8. UV-vis spectra of linkers METHODS: UV-vis spectra of linkers were performed on a Mapada UV-6100 spectroscopy using 1 cm quartz optical cells. And linkers were dissolved as 0.1M solution in DMF. All UV-vis spectra exhibit sharp absorption peak at nm, typical for porphyrin motifs, and each spectrum shows characteristic band at nm (S11). Figure S33. UV-vis spectra of linkers in DMF. S48

49 Section S9. N 2 adsorptions analysis METHODS: All N 2 adsorptions experiments were measured on a Quantachrome Autosorb-1 automatic volumetric instrument. A liquid nitrogen bath (77k) was used for isotherm measurements. Ultra-high purity grade N 2 was used to the adsorption experiments. The BET analysis is performed by plotting x/v(1 - x) vs x, where x = P/P 0 (P 0 = 1 bar) and v is the volume of nitrogen adsorbed per gram of MOF at STP. This analysis produces a curve typically consisting of three regions: concave to the x axis at low pressures, linear at intermediate pressures, and convex to the x axis at high pressures. The slope ([c - 1]/v m c) and y intercept (1/v m c) of this linear region give the monolayer capacity, v m, that is then used to calculate the surface area from A = v m σ 0 N AV, where σ 0 is the cross-sectional area of the adsorbate at liquid density (16.2 Å 2 for nitrogen) and N AV is Avogadro s number (S12). Three single component SBU MOFs, (Ni 3 O) 2 (TCPP-Cu) 3, (Ni 3 O) 2 (TCPP-Co) 3, (Fe 3 O) 2 (TCPP-Co) 3 and one MTV-MOF, Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 were measured here. Type IV isotherms were observed for these MOFs, revealing their mesoporous nature. The BET surface area of (Ni 3 O) 2 (TCPP-Cu) 3, (Ni 3 O) 2 (TCPP-Co) 3, (Fe 3 O) 2 (TCPP-Co) 3 and (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 were calculated to be 2200, 2090, 1660 and 1380 m 2 /g, respectively. Pore size distributions for MOFs were analyzed using non-local density functional theory (NLDFT) based on a carbon model containing cylindrical pores. Estimated distributions for these MOFs are close to pore diameters calculated from refined crystal structures. S49

50 Figure S34. N 2 isotherm of (Ni 3 O) 2 (TCPP-Co) 3 at 77 K. Filled and open symbols represent adsorption and desorption branches, respectively. Insert, pore distribution of (Ni 3 O) 2 (TCPP-Co) 3. Figure S35. BET area calculation for (Ni 3 O) 2 (TCPP-Co) 3 from simulated nitrogen isotherm at 77 K (A) Only points between the dashed line are selected based on the first consistency criterion, (B) Plot to select linear P/P 0 range. S50

51 Figure S36. N 2 isotherm of (Ni 3 O) 2 (TCPP-Cu) 3 at 77 K. Filled and open symbols represent adsorption and desorption branches, respectively. Insert, pore distribution of (Ni 3 O) 2 (TCPP-Cu) 3. Figure S37. BET area calculation for (Ni 3 O) 2 (TCPP-Cu) 3 from simulated nitrogen isotherm at 77 K (A) Only points between the dashed line are selected based on the first consistency criterion, (B) Plot to select linear P/P 0 range. S51

52 Figure S38. N 2 isotherm of (Fe 3 O) 2 (TCPP-Co) 3 at 77 K. Filled and open symbols represent adsorption and desorption branches, respectively. Insert, pore distribution of (Fe 3 O) 2 (TCPP-Co) 3. Figure S39. BET area calculation for (Fe 3 O) 2 (TCPP-Co) 3 from simulated nitrogen isotherm at 77 K (A) Only points between the dashed line are selected based on the first consistency criterion, (B) Plot to select linear P/P 0 range. S52

53 Figure S40. N 2 isotherm of (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 at 77 K. Filled and open symbols represent adsorption and desorption branches, respectively. Insert, pore distribution of (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3. Figure S41. BET area calculation for (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 from simulated nitrogen isotherm at 77 K (A) Only points between the dashed line are selected based on the first consistency criterion, (B) Plot to select linear P/P 0 range. Table S20 Summary of gas adsorption for MOFs Compound (Ni 3 O) 2 (Ni 3 O) 2 (Fe 3 O) 2 (Mn 1.77 Ni 1.23 O) 2 (TCPP-Cu) 3 (TCPP-Co) 3 (TCPP-Co) 3 (TCPP-Ni) 3 S A BET experimental (m 2 /g) S A BET calculated (m 2 /g) Pore volume experimental (cm 3 /g) Pore volume calculated (cm 3 /g) S53

54 Section S10. Photo-oxidation reactions METHODS: 4mg MOF was added into 100 ml acetonitrile containing DHN ( M) solution. The solution was degassed for three times and pure O 2 was added. Then it was illuminated by a 300W xenon lamp (Perfectlight PLS-SXE300/300UV) and reaction started. As reaction goes on, 2mL reaction solution was taken out at special time. UV-vis spectra of these solutions were measured and reaction yields were calculated from absorption of Juglone. UV-vis spectra were performed on a Mapada UV-6100 spectroscopy using 1 cm quartz optical cells. Photo-oxidation of 1,5-Dihydroxynaphthalene (DHN) results in Dihydroxy-1,4- naphthoquinone (Juglone) (Fig. S42). UV-vis spectra were used to monitor the reaction. In which band at 298 nm is absorption of DHN and 420 nm is absorption of Juglone. As reaction goes on, absorption of DHN decreases and absorption of Juglone goes up. According to the previous reports, the reaction of DHN is a quasi-first order reaction, and it is a linear relationship of ln(a t /A 0 ) versus time. The slope (k obs ) of the line is observed reaction rate. Figure S42. Photo-oxidation reactions of DHN (top). Monitor protocol of this model reaction (down). (left) UV-vis spectra of reaction solution that 298 nm band corresponds to DHN and 420 nm band to Juglone. (middle) Contents change of DHN and Juglone versus reaction time. (right) ln(a t /A 0 ) change versus reaction time. And the slope of this line is conversion rate k obs. S54

55 Table S21. Conversion rates k obs ( 10-2 h -1 ) of MOFs with different combinations of SBU and linker. TCPP-H2 TCPP-Mg TCPP-Co TCPP-Ni TCPP-Cu Mg 3 O Mn 3 O Co 3 O Ni 3 O Fe 3 O Ni 2.46 Fe 0.54 O Ni 2.07 Fe 0.93 O Ni 1.50 Fe 1.50 O Ni 1.29 Fe 1.71 O Ni 3 O +Fe 3 O Ni 2.16 Co 0.84 O Mn 1.95 Co 1.05 O Mn 1.45 Fe 1.55 O Mn 2.52 Mg 0.48 O Mn 1.77 Ni 1.23 O S55

56 Figure S43. (left column) UV-vis spectra of photo-oxidation of DHN with time for (Mn 3 O) 2 (TCPP-M) 3. (middle column) Content changes of DHN and Juglone versus reaction time for (Mn 3 O) 2 (TCPP-M) 3. (right column) Plots of ln(a t /A 0 ) versus reaction time for (Mn 3 O) 2 (TCPP-M) 3. S56

57 Figure S44. Summary of ln(a t /A 0 ) versus irradiation time for (Mn 3 O) 2 (TCPP-M) 3. Photo-oxidation performance of (Mn 3 O) 2 (TCPP-M) 3 which has the same SBU metal but different linker-metals shows that different linker-metals exhibit different k obs. MOFs with TCPP-metal show higher conversion rates than that with TCPP-H 2. S57

58 Figure S45. (left column) UV-vis spectra of photo-oxidation of DHN with time for (M 3 O) 2 (TCPP-Co) 3 and TCPP-Co. (middle column) Content changes of DHN and Juglone versus reaction time for (M 3 O) 2 (TCPP-Co) 3 and TCPP-Co (right column) Plots of ln(a t /A 0 ) versus reaction time for (M 3 O) 2 (TCPP-Co) 3 and TCPP-Co. S58

59 Figure S46. Summary of ln(a t /A 0 ) versus irradiation time for (M 3 O) 2 (TCPP-Co) 3. In (M 3 O) 2 (TCPP-Co) 3 series, MOFs with Mn, Co, Ni and Mg SBUs show better performance than Fe SBU. S59

60 Figure S47. (left column) UV-vis spectra of photo-oxidation of DHN with time for (M 3 O) 2 (TCPP-Ni) 3. (middle column) Content changes of DHN and Juglone versus reaction time for (M 3 O) 2 (TCPP-Ni) 3. (right column) Plots of ln(a t /A 0 ) versus reaction time for (M 3 O) 2 (TCPP- Ni) 3. S60

61 Figure S48. Summary of ln(a t /A 0 ) versus irradiation time for (M 3 O) 2 (TCPP-Ni) 3. S61

62 Figure S49. (left column) UV-vis spectra of photo-oxidation of DHN with time for (Mn x M 3- xo) 2 (TCPP-Ni) 3. (middle column) Content changes of DHN and Juglone versus reaction time for (Mn x M 3-x O) 2 (TCPP-Ni) 3. (right column) Plots of ln(a t /A 0 ) versus reaction time for (Mn x M 3- xo) 2 (TCPP-Ni) 3. S62

63 Figure S50. Summary of ln(a t /A 0 ) versus irradiation time for (Mn x M 3-x O) 2 (TCPP-Ni) 3. S63

64 Figure S51. (left column) UV-vis spectra of photo-oxidation of DHN with time for (Ni x Fe 3- xo) 2 (TCPP-Co) 3. (middle column) Content changes of DHN and Juglone versus reaction time for (Ni x Fe 3-x O) 2 (TCPP-Co) 3. (right column) Plots of ln(a t /A 0 ) versus reaction time for (Ni x Fe 3- xo) 2 (TCPP-Co) 3. S64

65 Figure S52. Summary of ln(a t /A 0 ) versus irradiation time for (Ni x Fe 3-x O) 2 (TCPP-Co) 3. S65

66 XPS was used to measure the chemical environment of metals in MOF after catalysis. Binding energy of Mn, Fe and Ni of (Mn 1.35 Fe 1.65 O) 2 (TCPP-Ni) 3 after catalysis is identical to that of their counterparts before catalysis (Fig. S53), indicating the chemical environment of SBU-metal Mn, Fe and linker-metal Ni was maintained throughout the catalysis reaction. Figure S53. XPS of (Mn 1.35 Fe 1.65 O) 2 (TCPP-Ni) 3 before and after catalysis S66

67 Table S22. ICP data of (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 after catalysis Mn Ni Supernatant after catalysis not detectable not detectable (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 Additional ICP experiment has been done that no metal was detected in the supernatant of reaction solution, and it also indicates the stability of MOF in the catalysis reaction. Figure S54. ln(a t /A 0 ) versus irradiation time with error bar that each one was repeated twice. (A) (Mg 3 O) 2 (TCPP-Co) 3, (B) (Ni 2.16 Co 0.84 O) 2 (TCPP-Co) 3. S67

68 Section S11. X-ray adsorption spectra of MOFs In order to confirm the oxidation state of SBU metals in MOFs and further study the coordination environment of metals in MOFs after solvent removal and throughout the catalytic process, X-ray absorption spectroscopy (XAS) measurements were performed. Five MOFs (Fe 3 O) 2 (TCPP-Co) 3, (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3, (Mn 3 O) 2 (TCPP-Ni) 3, (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 and (Co 3 O) 2 (TCPP-Ni) 3 were selected as illustrative. Firstly, oxidation state of Fe in (Fe 3 O) 2 (TCPP-Co) 3 and (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 was measured by means of X-ray absorption near edge structure (XANES). Secondly, Extended X-ray absorption fine structure (EXAFS) analysis of SBU-metal Mn, Co and linker-metal Ni was performed, using MOFs (Mn 3 O) 2 (TCPP-Ni) 3, (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 and (Co 3 O) 2 (TCPP-Ni) 3, to gain insight into the coordination environment of metals in MOFs. Here, SC-XRD data of (Mn 3 O) 2 (TCPP-Co) 3, (Co 3 O) 2 (TCPP-Co) 3 and a SC-XRD data of porphyrin-ni (S13) were used as structure models for the EXAFS analysis. The unaltered coordination environment of metals in this series of MOF after solvent removal and catalytic cycle confirms the robustness of their structure (Fig. S58-71, Table S22-24). METHODS: XAS measurements were performed on the bending magnet beam line 14W1 and 15U at Shanghai Synchrotron Radiation Facility (SSRF). Samples were tableted as a 1 cm 2 square disk. Measurements were performed in transmission detection mode in air at room temperature. XANES and EXAFS analysis was performed using the Athena/Artemis/Hephaestus software package which makes use of IFEFFIT (S15). Athena was used for XAS data processing including conversion of raw data to μ(e) spectra, background subtraction, Fourier transforming and plotting. Artemis was used to analysis EXAFS data, including the range of the Fourier transform from k-space and the fitting range in R- space. And EXAFS fitting was calculated using the built-in FEFF function of Artmis based on structure model from SC-XRD data. XANES is a sensitive technology to determine the oxidation state of metals which adsorption edge show significant shifts (binding energy shifts) with oxidation state. Adsorption edge of Fe in (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 and (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 match well with that of the reference of Fe(acac) 3 (Fe 3+ ) but difference with Fe(ac) 2 (Fe 2+ ), suggesting the oxidation states of Fe is +3 in both (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 and (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 (Fig. S55). Adsorption edge of Mn in (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 and (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 which is good agreement with that of the reference of Mn(acac) 2 (Mn 2+ ) but difference with Mn 2 O 3 (Mn 3+ ), suggesting the oxidation states of Mn is +2 in both (Mn 1.77 Ni 1.23 O) 2 (TCPP-Ni) 3 and (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 (Fig. S56). Adsorption edge of Ni in (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 is consistent with that of the reference of Ni(acac) 2 (Ni 2+ ), suggesting the oxidation state of Ni is +2 in (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 (Fig. S57). S68

69 Figure S55. K-edge XANES data of (1) Fe(ac) 2, (2) Fe(acac) 3 as standard, in green and black, respectively, and the MOF samples (4) (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 and (Mn 1.45 Fe 1.55 O) 2 (TCPP- Ni) 3 in red and blue. Figure S56. K-edge XANES data of (1) Mn(acac) 2, (2) Mn 2 O 3 as standard, in green and blue, respectively, and the MOF samples (4) (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 and (Mn 1.77 Fe 1.23 O) 2 (TCPP- Ni) 3 and in black and red. S69

70 Figure S57. K-edge XANES data of Ni(acac) 2 as standard in black, and the MOF sample (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 in red. S70

71 Figure S58. (A) K-edge of Mn for (Mn 3 O) 2 (TCPP-Ni) 3. (B) k-space EXAFS spectra for (Mn 3 O) 2 (TCPP-Ni) 3. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S71

72 Figure S59. (A) K-edge of Mn for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 before catalysis. (B) k-space EXAFS spectra for (Mn 3 O) 2 (TCPP-Ni) 3 before catalysis. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S72

73 Figure S60. (A) K-edge of Mn for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 after catalysis. (B) k-space EXAFS spectra for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 after catalysis. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S73

74 Quantitative information about the coordination environment of SBU-metal Mn in these MOFs calculated from EXAFS (Fig. S58-S60) and structure information from SC-XRD data of (Mn 3 O) 2 (TCPP-Co) 3 are listed in Table S23. Mn-O and Mn-C distances and coordination number of Mn calculated from XAS experiment are identical with that measured from SC-XRD, indicating the maintenance of the coordination environment of SBU-metal Mn in (Mn 3 O) 2 (TCPP-Ni) 3 and (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 throughout the activation. Furthermore, coordination environment of SBU-metal Mn in (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 was maintained during the catalysis, since coordination environment of SBU-metal Mn after catalysis was the same as that before catalysis. Figure S61. Coordination environment of SBU-metal Mn from SC-XRD data of (Mn 3 O) 2 (TCPP- Co) 3. Table S23. Coordination environment parameters of Mn yielded from EXAFS SC-XRD data a (Mn 3O) 2(TCPP-Ni) 3 (Mn 1.95Co 1.05O) 2(TCP P-Ni) 3 before catalysis (Mn 1.95Co 1.05O) 2(TCP P-Ni) 3 after catalysis R b CN c R b CN c R b CN c R b CN c Mn-O Mn-O Mn-O Mn-C a SC-XRD data from (Mn 3O) 2(TCPP-Co) 3, b Interatomic distance, c Coordination number. S74

75 Figure S62. (A) K-edge of Co for (Co 3 O) 2 (TCPP-Ni) 3. (B) k-space EXAFS spectra for (Co 3 O) 2 (TCPP-Ni) 3. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S75

76 Figure S63. (A) K-edge of Co for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 before catalysis. (B) k-space EXAFS spectra for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 before catalysis. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S76

77 Figure S64. (A) K-edge of Co for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 after catalysis. (B) k-space EXAFS spectra for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 after catalysis. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S77

78 Quantitative information about the coordination environment of SBU-metal Co in these MOFs calculated from EXAFS (Fig. S62-S64) and structure information from SC-XRD data of (Co 3 O) 2 (TCPP-Co) 3 are listed in Table S24. The Co-O and Co-C distances and coordination number of SBU-metal Co calculated from XAS experiment are identical with that measured from SC-XRD, indicating the maintenance of the coordination environment of SBU-metal Co in (Co 3 O) 2 (TCPP- Ni) 3 and (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 throughout the activation. Furthermore, coordination environment of SBU-metal Co in (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 was maintained during the catalysis, since coordination environment of SBU-metal Co after catalysis was the same as that before catalysis. Figure S65. Coordination environment of SBU-metal Co from SC-XRD data of (Co 3 O) 2 (TCPP- Co) 3. Table S24. Coordination environment parameters of Co yielded from EXAFS SC-XRD data a (Co 3O) 2(TCPP-Ni) 3 (Mn 1.95Co 1.05O) 2(TCP P-Ni) 3 before catalysis (Mn 1.95Co 1.05O) 2(TCP P-Ni) 3 after catalysis R b CN c R b CN c R b CN c R b CN c Co-O Co-O Co-O Co-C a SC-XRD data from (Co 3O) 2(TCPP-Co) 3, b Interatomic distance, c Coordination number. S78

79 Figure S66. (A) K-edge of Ni for (Mn 3 O) 2 (TCPP-Ni) 3. (B) k-space EXAFS spectra for (Mn 3 O) 2 (TCPP-Ni) 3. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S79

80 Figure S67. (A) K-edge of Ni for (Co 3 O) 2 (TCPP-Ni) 3. (B) k-space EXAFS spectra for (Co 3 O) 2 (TCPP-Ni) 3. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S80

81 Figure S68. (A) K-edge of Ni for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 before catalysis. (B) k-space EXAFS spectra for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 before catalysis. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S81

82 Figure S69. (A) K-edge of Ni for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 after catalysis. (B) k-space EXAFS spectra for (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 after catalysis. (C) real part of R space, (D) imaginary part of R-space, and (E) magnitude of R-space. Black line: experiment one, red line: fit one. S82

83 Quantitative information about the coordination environment of linker-metal Ni in these MOFs calculated from EXAFS (Fig. S66-S69) and structure information from porphyrin-ni (CCDC number: ) are listed in Table S25. The atomic distances of Ni-N and Ni-C and coordination number of Ni calculated from XAS experiment are identical with that measured from SC-XRD, indicating no change of the coordination environment of linker-metal Ni in (Mn 3 O) 2 (TCPP-Ni) 3, (Co 3 O) 2 (TCPP-Ni) 3 and (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 after activation. Furthermore, (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 is stable during the catalysis, since coordination environment of linker-metal Ni after catalysis was the same as that before catalysis. It is corresponding to the data of SBU-metal Mn and Co (Table S22-S24). Figure S70. Coordination environment of linker-metal Ni from SC-XRD data of porphyrin-ni. Table S25. Coordination environment parameters of Ni yielded from EXAFS Porphyrin-Ni a (Co 3O) 2(TCPP-Ni) 3 (Co 3O) 2(TCPP-Ni) 3 (Mn 1.77Ni 1.23O) 2(TCP P-Ni) 3 before catalysis (Mn 1.77Ni 1.23O) 2(TCP P-Ni) 3 after catalysis R b CN c R b CN c R b CN c R b CN c R b CN c Ni-N Ni-N Ni-C Ni-C a SC-XRD from porphyrin-ni, b Interatomic distance, c Coordination number. S83

84 Section S12. Electron Paramagnetic Resonance (EPR) of MOFs Electron paramagnetic resonance (EPR) data were collected to confirm oxidation state of SBU metals in MOFs. And it was collected in High Magnetic Field Laboratory of the China Academy of Sciences in Hefei (CHMFL). EPR spectra of (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 was measured to oxidation state of Mn and Co in it. Spectrum of Mn shows typical EPR of Mn with +2 oxidation state, 6 lines due to the hyperfine interactions of Mn 2+ ions with g factor 2.037(85). Spectrum of Co shows typical EPR of Co with +2 oxidation state, with g factor 4.394(81) (S16). Figure S71. EPR spectra of (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3. (A) EPR data of Mn in (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 recorded at 9.3 GHz and at room temperature, and (B) EPR data of Co in (Mn 1.95 Co 1.05 O) 2 (TCPP-Ni) 3 recorded at 9.3 GHz and at 2K. S84

85 Section S Fe Mössbauer spectroscopy of MOFs To probe the oxidation state of SBU-metal Fe in MTV-MOFs, room temperature 57 Fe Mössbauer spectra of MTV-MOFs (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 and (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3 were recorded with a constant acceleration spectrometer equipped with a 57 Co source diffused into an Rh matrix. The velocity was calibrated at 295 K with α-fe foil as standard and all the spectra were collected in the transmission mode. The absorber consists of MOF powders of about 40 mg/cm 2. The experimental spectra were fitted with appropriate super-positions of Lorentzian lines using the MossWinn 3.0i program. In this way, the important hyperfine parameters, such as isomer shift (IS), electric quadrupole splitting (QS), effective magnetic field (H), could be determined. Figure S72. (A) Mössbauer spectra of MTV-MOFs (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3. (B) Mössbauer spectra of MTV-MOFs (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3. The spectrum of (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3 shows only a sharp doublet adsorption characterized by an isomer shift (δ) of 0.37(4) mm/s, a quadrupole splitting 2+ of 0.80(1) mm/s and a line width 0.60(4) mm/s. Obviously there is no Fe ( E ) Q absorption side peak present and hence indicating all Fe locate in one kind coordination environment and all +3 oxidation state of SBU-metal Fe in MTV-MOF (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) 3. The spectrum of (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3 shows only a sharp doublet adsorption characterized by an isomer shift (δ) of 0.39(2) mm/s, a quadrupole splitting 2+ of 0.80(4) mm/s and a line width 0.59(2) mm/s. Obviously there is no Fe ( E ) Q absorption side peak present and hence indicating all Fe locate in one kind coordination environment and all +3 oxidation state of SBU-metal Fe in MTV-MOF (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) 3. Table S26. Mössbauer spectra parameter of MOFs Δ (mm/s) E Q (mm/s) line width (mm/s) (Mn 1.45 Fe 1.55 O) 2 (TCPP-Ni) (4) 0.80(1) 0.60(4) (Ni 1.50 Fe 1.50 O) 2 (TCPP-Co) (2) 0.80(4) 0.59(2) S85

86 Section S14. Ultraviolet-visible diffuse reflectance spectra (UV-vis DRS) of MOFs METHODS: UV-vis DRS of MOFs were performed on a PerkinElmer Lambda 750 S spectroscopy using BaSO 4 as background (S17). Band gap calculations were based on Kubleka-Munk theory. The optical absorption coefficient (α) calculated from reflectance data according to Kubelka-Munk equation that F(R) = α= (1-R) 2 /2R, in which R is the percentage of reflected light. The incident photon energy (hν) and the optical band gap energy (Eg) are related to the transformed Kubelka-Munk function, [F(R)hν] 2 = A(hν Eg), where Eg is the band gap energy, A is the constant depending on transition probability, and intercept of [F(R)hν] 2 vs hv is Eg. Eg of these MOFs range from ev (Fig. S73-S78), which is consistent with data of reported porphyrin-mofs (S18). According to the common sense, light with larger energy than the band gaps of MOFs could be efficiently used in the catalysis reaction. Thus, the overlaps between Xe lamp emission spectra and absorption spectra of MOFs are calculated here. And the cutoff is the band gap of MOFs (Fig. S79-S80). In the case of MTV-MOFs with the domain metal arrangement, (Mn 1.35 Fe 1.65 O) 2 (TCPP-Ni) 3 and its single component counter parts, (Mn 3 O) 2 (TCPP-Ni) 3, (Fe 3 O) 2 (TCPP-Ni) 3 exhibit almost identical band gap (Fig. 3F). Thus the difference in their catalytic conversion rate is determined by their lightharvesting ability. The conversion rate follows the order of (Mn 3 O) 2 (TCPP-Ni) 3 > (Mn 1.35 Fe 1.65 O) 2 (TCPP-Ni) 3 > (Fe 3 O) 2 (TCPP-Ni) 3, in good agreement with their light-harvesting ability (Table S27). In contrast, in the case of MTV-MOFs with the well-mixed metal arrangement, although there are slight difference in the light harvesting ability, (Ni 3 O) 2 (TCPP- Co) 3 > (Fe 3 O) 2 (TCPP-Co) 3 > (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 (Fig. S80), the band gap is the dominating factor. Since the band gap of (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 matches better with the oxygen reduction, in comparison to (Ni 3 O) 2 (TCPP-Co) 3 and (Fe 3 O) 2 (TCPP-Co) 3 (Fig. 3F), the order of catalysis performance reflected in their conversion rates follows the same trend. Table S27. Light-harvest ability and k obs summary of MOFs (Mn 3 O) 2 (TCPP-Ni) 3 (Mn 1.35 Fe 1.65 O) 2 (TCPP-Ni) 3 (Fe 3 O) 2 (TCPP-Ni) 3 Light-absorb ability 57.9% 54.7% 51.9% k obs ( 10-2 h -1 ) S86

87 Figure S73. (A) UV-vis reflectance spectrum of (Mn 3 O) 2 (TCPP-Ni) 3, (B) The band gap of (Mn 3 O) 2 (TCPP-Ni) 3 estimated from UV-vis reflectance spectrum. S87

88 Figure S74. (A) UV-vis reflectance spectrum of (Fe 3 O) 2 (TCPP-Ni) 3, (B) The band gap of (Fe 3 O) 2 (TCPP-Ni) 3 estimated from UV-vis reflectance spectrum. S88

89 Figure S75. (A) UV-vis reflectance spectrum of (Mn 1.35 Fe 1.65 O) 2 (TCPP-Ni) 3, (B) The band gap of (Mn 1.35 Fe 1.65 O) 2 (TCPP-Ni) 3 estimated from UV-vis reflectance spectrum. S89

90 Figure S76. (A) UV-vis reflectance spectrum of (Ni 3 O) 2 (TCPP-Co) 3, (B) The band gap of (Ni 3 O) 2 (TCPP-Co) 3 estimated from UV-vis reflectance spectrum. S90

91 Figure S77. (A) UV-vis reflectance spectrum of (Fe 3 O) 2 (TCPP-Co) 3, (B) The band gap of (Fe 3 O) 2 (TCPP-Co) 3 estimated from UV-vis reflectance spectrum. S91

92 Figure S78. (A) UV-vis reflectance spectrum of (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3, (B) The band gap of (Ni 2.07 Fe 0.93 O) 2 (TCPP-Co) 3 estimated from UV-vis reflectance spectrum. S92

93 Figure S79. Overlap percentages between Xe lamp emission spectra and absorption spectra of MOFs. Cutoff is the position for the band gap of MOFs. Black line is Xe lamp emission spectra. Red line is MOFs absorption spectra. S93

94 Figure S80. Overlap percentages between Xe lamp emission spectra and absorption spectra of MOFs. Cutoff is the position for the band gap of MOFs. Black line is Xe lamp emission spectra. Red line is MOFs absorption spectra. S94