Supporting Information

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1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2018 Supporting Information Fig. S1 TGA curves of UiO-67, RuOH and RhOH Fig. S2 FT-IR spectras of UiO-67, RuOH and RhOH

2 Fig. S3 UV-vis absorption spectra of Ru(bpy) 3Cl 2, H 2RuCl, H 2RuOH 2, H 2RhCl and H 2RhOH 2 in DMF solution ( mol l -1 ). Fig. S4 Diffuse reflection UV-vis absorption spectra of UiO-67, RuCl@UiO, RuOH 2@UiO, RhCl@UiO and RhOH 2@UiO.

3 Fig. S5 PXRD patterns of RhOH before and after 174 h photocatalytic hydrogen evolution experiments in different DMF/H 2O solution. Fig. S6 PXRD patterns for PSE-MOFs after 6 h photocatalytic CO 2 reduction experiments.

4 Fig. S7 Photoluminescence spectra of (Ru(bpy) 3Cl 2, 4 mg) in a mixed solution of 5mL DMF/H 2O (v/v, 4/1). And changing spectra after 0.3 μmol H 2RuCl, H 2RuOH 2, H 2RhCl or H 2RhOH 2 was added into the solution, respectively. Fig. S8 Photoluminescence spectra of (Ru(bpy) 3Cl 2, 4 mg) in a mixed solution of 5 ml DMF/H 2O (v/v, 4/1). And changing spectra after 0.2 and 1 ml TEOA was added into the solution.

5 Fig. S9 Photoluminescence spectra of (Ru(bpy) 3Cl 2, 4 mg) in a mixed solution of 5mL DMF/H 2O (v/v, 4/1). And changing spectra after 0.2 and 0.4 ml DMA was added into the solution. Fig. S10 The cyclic voltammograms (CVs) of 1mM H 2RuCl, H 2RuOH 2, H 2RhCl and H 2RhOH 2 in DMF solvent.

6 Table S1 Crystal data for H 2RuCl and H 2RhOH 2 complex. Complex H 2RuCl H 2RhOH 2 Temperature 150 K 150 K Chemical formula C 22H 24Cl 2N 2O 5Ru C 44H 56N 8O 25Rh 2 CCDC number Formula weight crystal system Triclinic Monoclinic space group P-1 P2 1 a (Å) (3) (1) b (Å) (3) (2) c (Å) (4) (2) α (deg) (3) 90 β (deg) (3) (1) γ (deg) (3) 90 V (Å 3 ) (6) (5) Z 2 2 D Calcd (g cm -3 ) μ (mm -1 ) Ref. collected Independent ref R int Goodness of fit R1 a [I > =2 (I)] b wr 2 [I > =2 (I)] a R 1= ( F 0 - F c )/ F 0 ; b wr 2=[ w(f 02 - F c2 ) 2 / w(f 02 ) 2 ] 1/2

7 Table S2 Hydrogen evolution performance of some similar molecule catalyst systems by incorporating catalyst into MOF frameworks. a MOFs Photosensitizer Catalyst TON Amount RhOH 2@UiO (This work) Ru(bpy) 3Cl 2 [Rh(Cp*)(bpydc) 470 (174 h) μmol (174 h) (OH 2)](NO 3) 2 Pt 0.1_Ir_BuiO S[1] [Ir(ppy) 2(bpydc)] - Na + Pt/ H 2Pt(bpydc)Cl (156 h) 11.9μmol (156 h) Ru-Pt@UiO-67 S[2] H 2Ru(bpydc)(bpy) 2 H 2Pt(bpydc)Cl 2 >0.5 μmol (5 h) UiO-66-[FeFe]- (dcbdt)(co) 6 S[3] a dcbdt= 1,4-dicarboxylbenzene-2,3-dithiolate. Ru(bpy) 3Cl 2 H 2[FeFe](dcbdt)(CO) 6 ~3.5μmol (2.5 h) Table S3 CO 2 photo-reduction performance of some similar molecule catalyst systems by incorporating catalyst into MOF frameworks. a MOFs Photosensitizer Catalyst TON (CO) TON (H 2) TON (HCOO - ) TON(HCOO - ) /TON(CO) RhCl@UiO Ru(bpy) 3Cl 2 [Rh(Cp*)(bpydc) (This work) (Cl)]Cl H 2O {Zr 6(O) 4(OH) 4- Re(CO) 3Cl(bpyd Re(CO) 3Cl(bpydb) [Re(CO) 3Cl(bpydb)] 6} S[4] b) {Zr 6(O) 4(OH) 4- Re(bpydc)(CO) 3 Re(bpydc)(CO) 3Cl [Re(CO) 3Cl(bpydc)] 6} S[5] Cl Zr 6O 4(OH) 4(Mn(bpydc) (CO) 3Br) 2.3(bpydc) 0.7(bpdc) Ru(dmb) 3](PF 6) 2 Mn(bpy)(CO) 3Br S[6] MOF-253-Ru(CO) 2Cl S[7] 2 Ru(CO) 2Cl 2 Ru(bpydc)(CO) 2Cl Cp*Rh@UiO-67 S[8] Ru(bpy) 3Cl 2 Cp*Rh(bpydc)Cl Zr-bpdc/RuCO S[9] [Ru(bpy) 3](PF 6) 2 [Ru(H 2bpydc)(terpy) (CO)](PF 6) a Bpydb= 4,4 -(2,2 -bipyridine-5,5 -diyl)dibenzoate, dmb= 4,4 -dimethyl-2,2 -bipyridine, terpy= 2,2 : 6,2 -terpyridine. Table S4 Photocatalytic CO 2 reduction results for RuCl@UiO, RuOH 2@UiO, RhCl@UiO and RhOH 2@UiO under CO 2 atmosphere by a LED lamp. a Entry Catalyst Sacrificial agent TON (CO) TON (H 2) TON (HCOO - ) TON(HCOO - ) /TON (CO) S22 RuCl@UiO TEOA 0.1 ml S23 RuOH 2@UiO TEOA 0.1 ml S24 RhCl@UiO TEOA 0.1 ml S25 RhOH 2@UiO TEOA 0.1 ml S26 RuCl@UiO DMA 1 ml < S27 RuOH 2@UiO DMA 1 ml < S28 RhCl@UiO DMA 1 ml S29 RhOH 2@UiO DMA 1 ml a Conditions: Photosensitizer (Ru(bpy) 3Cl 2, 4 mg), Photocatalyst (4 mg), sacrificial agent, solvents (MeCN 5 ml), CO 2 bubbling for 20 min, and irradiation with a 100 W LED lamp for 6 h.

8 Table S5 Electrochemical potentials (E 1/2 vs.ag/agcl) of 1mM H 2RuCl, H 2RuOH 2, H 2RhCl and H 2RhOH 2 in DMF solvent. Complex a E 1/2(ox) / V vs. Ag/AgCl E 1/2(red) / V vs. Ag/AgCl b H 2RuCl ir , ir, ir H 2RuOH ir , ir, ir H 2RhCl ir , ir, H 2RhOH ir , ir, a Measured conditions: Ag/AgCl was as reference electrode, glassy carbon was as working electrode, and platinum plate was as counter electrode. Solvent: DMF, electrolyte: Bu 4NPF 6 (0.1 M), scan rate: 0.1 V/s. ir = irreversible. b Translation to values vs. NHE: Supplementary References [1] D. Kim, D. R. Whang, S. Y. Park, Journal of the American Chemical Society 2016, 138, [2] C.-C. Hou, T.-T. Li, S. Cao, Y. Chen, W.-F. Fu, J. Mater. Chem. A 2015, 3, [3] S. Pullen, H. Fei, A. Orthaber, S. M. Cohen, S. Ott, J. Am. Chem. Soc. 2013, 135, [4] R. Huang, Y. Peng, C. Wang, Z. Shi, W. Lin, Eur. J. Inorg. Chem. 2016, 2016, [5] C. Wang, Z. Xie, K. E. dekrafft, W. Lin, J. Am. Chem. Soc. 2011, 133, [6] H. Fei, M. D. Sampson, Y. Lee, C. P. Kubiak, S. M. Cohen, Inorg. Chem. 2015, 54, [7] D. Sun, Y. Gao, J. Fu, X. Zeng, Z. Chen, Z. Li, Chem. Commun. 2015, 51, [8] M. B. Chambers, X. Wang, N. Elgrishi, C. H. Hendon, A. Walsh, J. Bonnefoy, J. Canivet, E. A. Quadrelli, D. Farrusseng, C. Mellot-Draznieks, M. Fontecave, ChemSusChem 2015, 8, [9] T. Kajiwara, M. Fujii, M. Tsujimoto, K. Kobayashi, M. Higuchi, K. Tanaka, S. Kitagawa, Angew. Chem., Int. Ed. 2016, 55,