Electronic Supplementary Information prepared for Dalton Transactions

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1 Electronic Supplementary Information prepared for Dalton Transactions Address correspondence to: Seiji go, Professor International Institute for Carbon Neutral Energy Research (WPI-ICNER), Kyushu University 744 Moto oka, Nishi ku, Fukuoka , Japan Phone: Fax: A model for the water-oxidation and recovery systems of the oxygen-evolving complex

2 A table of contents Fig. S1 Fig. S Fig. S Fig. S4 Fig. S5 Fig. S6 Fig. S7 Fig. S8 Fig. S9 Fig. S10 Fig. S11 Fig. S1 Fig. S1 Fig. S14 Fig. S15 Fig. S16 page S1 page S page S page S4 page S5 page S6 page S7 page S8 page S9 page S10 page S11 page S1 page S1 page S14 page S15 page S16

3 + LMn II N(CH=CH )Et + H 1 (m/z 565.) hv Photoinhibition Recovery NEt + + (m/z 61.0) Fig. S1 Positive-ion ESI mass spectral change for the repeated cycle of photoreduction of and oxygenation of 1. The spectra of 1 shown in (b), (d) and (f) were obtained from photo-irradiation of shown in (a), (c) and (e), respectively. The spectra of shown in (c), (e) and (g) were obtained from oxygenation of 1 shown in (b), (d) and (f), respectively. (h) The signal at m/z 61.0 corresponds to [] +. (i) Calculated isotopic distribution for [] +. (j) The signal at m/z 565. corresponds to [1] +. (k) Calculated isotopic distribution for [1] +. S1

4 LMn II Electronic Supplementary Material (ESI) for Dalton Transactions + N(CH=CH )Et + H 1 18 hv Photoinhibition Recovery NEt labelled (m/z 6.0) Fig. S (a) Positive-ion ESI mass spectrum of in CH CN, which is obtained from the photo-irradiation of and successive oxygenation of 1. (b) The signal at m/z 61.0 corresponds to [] +. (c) Calculated isotopic distribution for [] +. (d) Positive-ion ESI mass spectrum of [Mn III,III (TPA) (µ- 18 ) ] + ( 18 -labelled ) in CH CN, which is obtained from the photo-irradiation of and successive oxygenation of 1 using 18. (b) The signal at m/z 6.0 corresponds to [ 18 -labelled ] +. S

5 N(CH=CH )Et + H NEt + hv Fig. S UV-vis spectra of,5-di-t-butyl-1,-benzoquinone (DTBBQ) (400 µm) and NEt (4.0 mm) in CH CN (.5 ml) (a) before and (b) after photo-irradiation (>550 nm). S

6 + LMn II N(CH=CH )Et + H hv Photoinhibition Recovery NEt + + Fig. S4 Positive-ion GC-mass spectra of H 16 and H 18 obtained from the reaction of (1.4 mg, 1.0 µmol) with (a) 16 (5.0 ml) and (b) 18 (5.0 ml) in the presence of,5-di-t-butyl-1,-benzoquinone (DTBBQ) ( mg, 100 µmol) and NEt (140 µl, 1.0 mmol) in CH CN (00 µl) under photo-irradiation (>550 nm). S4

7 + clay + Fig. S5 Diffuse reflectance UV-vis spectra of and (b) clay. S5

8 + clay + Fig. S6 ESR spectrum (5.0 mg, content of the mixture of and : 00 nmol) suspended in DMF (500 µl) at 150 ºC (microwave frequency: 9.16 GHz, microwave power: 1.0 mw). S6

9 + clay + Fig. S7 XRD patterns of and (b) clay. S7

10 + + 4H + + H LMn IV 4 (on clay) 4+ + Water-oxidation + (a) 100 nm STEM Mn N Mg (b) 100 nm STEM Mn N Mg Fig. S8 STEM images and EDS elemental mappings of and (b) clay material isolated from the mixture and. S8

11 Electronic Supplementary Material (ESI) for Dalton Transactions (without clay) 4+ MnIVL LMnIV + [CeIV,IV (N )10 (µ-)]4 MnIVL LMnIII 4 CeIII (Cl 4 ) CeIV Fig. S9 RTEP drawing of [CeIV,IV(N)10(µ-)]4 with ellipsoids at 50% probability. The counter cation [MnIV,IV(TPA)(µ-)]4+ (4) is omitted for clarity. Selected interatomic distance (l/å) and angle (φ/º): Ce1 =.0480(), Ce1 Ce1* = (11). S9

12 + Fig. S10 UV-vis spectra of (a) the CH CN solution of (100 µm) and (b) the supernatant CH CN/water solution after adsorption of on clay. S10

13 LMn IV Fig. S11 UV-vis spectra of (a) the aqueous solution of 4 (1.0 mm) and (b) the supernatant aqueous solution after adsorption of 4 on clay. S11

14 (on clay) LMn IV Fig. S1 XRD patterns of and (b) 4@Clay. S1

15 + + 4H + + H LMn IV 4 (on clay) 4+ + Water-oxidation + (start) Fig. S1 Time course of the evolved from the aqueous suspension (.0 ml) (600 µg, content of : 9 nmol) with an excess amount of (NH 4 ) [ (N ) 6 ] (17 mg, 50 µmol). S1

16 + + 4H + + H + Water-oxidation (on clay) LMn IV Mn VII 4 Fig. S14 UV-vis spectra of the supernatant solution (.0 ml) of the reaction (0 mg, content of :.0 µmol) with an excess amount of (NH 4 ) [ (N ) 6 ] (74 mg, 0.50 mmol) after (a) 0.5 min and (b) 60 min. S14

17 4+ LMn IV H + + H 18 Water-oxidation (on clay) 4 (start) + Fig. S15 Positive-ion GC mass spectrum of 16,18 and 18 obtained from the H 18 suspension (100 µl) (15 mg, content of : 980 nmol) and (NH 4 ) [ (N ) 6 ] (7 mg, 49 µmol). S15

18 H + + H 18 Water-oxidation (on clay) 4+ LMn IV 4 (start) + Fig. S16 Positive-ion GC mass spectrum of 16,18 and 18 obtained from the H 18 suspension (100 µl) of 4@Clay (50 mg, content of 4: 1.0 µmol) and (NH 4 ) [ (N ) 6 ] (7 mg, 49 µmol). S16