Section S1 Experimental Section

1. Materials and measurements

All chemicals were reagent grade quality obtained from commercial sources and used without any further  purification. The precursor H3PMo12O40·xH2O and H4SiW12O40·xH2O were synthesized according to the literature 1,2 and further confirmed by IR spectroscopy. Powder X-ray diffraction (PXRD) patterns were obtained by employing a  Bruker D8 ADVANCE diffractometer with Cu Kα radiation (the value of λ is 1.54056 Å). IR spectra were conducted  on a Bruker VERTEX 70 IR spectrometer (KBr pellets) recording in the range of 4000–450 cm−1 . TG analyses were  measured by a Perkin-Elmer TGA7 instrument under flowing N2 (heating rate, 10 °C·min−1 ). Elemental analyses (C,  H, N) were conducted on an Elementar Vario MICRO analyzer. The quantitative analyses of Cd, P, Si, Mo, W, Ru  elements and the filtrate after the removal of the catalyst were achieved by PerkinElmer Optima 2100 DV inductively  coupled plasma optical emission spectrometer (ICP). X-ray photoelectron spectroscopy (XPS) was performed with  an Axis Ultra X-ray photoelectron spectroscope equipped with monochromatic Al Kα (1486.7 eV) radiation. UVVisible diffuse reflectivity spectroscopy (DRS) was performed on UV-2600 using the BaSO4 powder as the reference. The steady state and time-resolved decay photoluminescence spectra (PL) were recorded on fluorescence  spectrophotometer (Hitachi F-7000) and photoluminescence spectrometer (Edinburg FLS1000), respectively. 1H  NMR spectra were recorded on Bruker AVANCE NEO 500 MHz NMR spectrometer, and the chemical shifts are  reported in ppm relative to DMSO (d = 2.5) for 1H NMR. The photocatalytic reaction was performed on WATTCAS  Parallel Light Reactor (WP-TEC-1020HSL) with a 10 W COB LED. The products were confirmed by GC-MS  (Agilent 7890B GC/5973B MS, SE-54 capillary column) and GC calculations of yields were performed on Bruker  450-GC with a flame ionization detector equipped with a 30 m column (GsBP-1) with nitro gen as carrier gas.

2. X-ray crystallography

The single crystals PMo-1 and SiW-2 were directly fixed on a loop and kept at 150.0 K during data collection  on a Bruker D8 VENTURE PHOTON II CCD diffractometer with Mo Kα radiation (the value of λ is 0.71073 Å).  The structure was solved with the ShelXT structure solution program using Intrinsic Phasing and further refined by  the full-matrix least-squares method on F2 using the ShelXL refinement package within Olex2.3 In addition, all the  atoms were refined anisotropically in the final refinement cycle, only a few harsh constraints have been used to  eliminate the ADP alert of a few atoms. And some disorders DMF were determined by the TGA results and element  analyses. The results show that PMo-1 contains 5 DMF, SiW-2 contains 4 DMF. Crystallographic data of PMo-1 and SiW-2 have been deposited in the Cambridge Crystallographic Data Center with CCDC numbers:  2115618−2115619. The crystallographic data and structure refinement parameters are shown in Table S1−3.

3. Synthesis of [Ru(bpy)2(H2dcbpy)]Cl2

[Ru(bpy)2(H2dcbpy)]Cl2 was synthesized according to the published synthesis procedure with some  modifications.4,5 [Ru(bpy)2Cl2] (800 mg,1.65 mmol) and (2,2’-bipyridine)-5,5’-dicarboxylic acid (505 mg, 2.1 mmol)  were mixed in 100 mL of EtOH/H2O(1:1, v/v), and refluxed for 24 hours under Ar atmosphere. After cooling to room  temperature the solvents were removed, and the solid was recrystallized from 100 mL of MeOH/diethyl ether (1:1,  v/v) mixture.  1H NMR (500 MHz, DMSO-d6, ppm): δ 9.01 (d, J = 8.4 Hz, 2H), 8.91 (d, J = 8.2 Hz, 2H), 8.87 (d, J =  8.2 Hz, 2H), 8.52 (dd, J = 8.4, 1.4 Hz, 2H), 8.24 (t, J = 7.4 Hz, 2H), 8.18 (t, J = 7.4 Hz, 2H), 8.01 (d, J = 1.2 Hz, 2H),  7.85 (d, J = 5.3 Hz, 2H), 7.79 (d, J = 5.4 Hz, 2H), 7.60 (t, J = 6.4 Hz, 2H), 7.53 – 7.49 (m, 2H)

4. The reactive radical scavenging experiments

5.1 The calculation of Turnover number (TON) and Turnover frequency (TOF)

The apparent quantum yield (AQY) is determined using a similar method to that for the photocatalytic  performance test. Test conditions: Benzylamine (1 mmol), Catalyst (1 μmol, 0.1 mol%), acetonitrile (1 mL), O2 (1  atm), 10 W 450 nm LED lamp. The intensity of the incident light was 550 mW·cm-2 , which was tested by a  photometer (CEL-NP2000-2A, Beijing CEAulight Co., Ltd., China), the irradiated area is 2 cm2 , and 98.7% of imine  was yielded after 30 minutes.

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