Supporting Information

On the synthesis and characterisation of luminescent hybrid particles: Mo6 metal cluster complex / SiO2Yuri A. Vorotnikov,ab Olga A. Efremova,*c Natalya A. Vorotnikova,ab Konstantin A. Brylev,abd Mariya V. Edeleva,be Alphiya R. Tsygankova,ad Anton I. Smolentsev,ad Noboru Kitamura,f Yuri V. Mironovad and Michael A. Shestopalov*abd

aNikolaev Institute of Inorganic Chemistry SB RAS, 3 Acad. Lavrentiev ave., 630090 Novosibirsk, Russian Federation.bScientific Institute of Clinical and Experimental Lymphology, 2 Timakova st., 630060 Novosibirsk, Russian Federation.cDepartment of Chemistry, University of Hull, Cottingham Road, Hull, UK, HU6 7RX.dNovosibirsk State University, 2 Pirogova st., 630090 Novosibirsk, Russian Federation.eNovosibirsk Institute of Organic Chemistry SB RAS, 9 Acad. Lavrentiev ave., 630090 Novosibirsk, Russian Federation.fDepartment of Chemistry, Faculty of Science, Hokkaido University, 060-0810 Sapporo, Japan

*Corresponding Authors:Michael A. ShestopalovTel. +7-383-330-92-53, Fax +7 (383) 330-94-89eMail: shtopy@niic.nsc.ru

Olga A. EfremovaTel. +44 (0)1482 465417eMail: o.efremova@hull.ac.uk

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016

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Content

1. Experimental Section …………………………………………………………………………...S3

2. FTIR spectra of precipitates An and Bn ………………………………………………………S4

3. FTIR spectra of the neat and cluster-doped SMPs …………….…………………….………S5

4. X-ray powder diffractograms of precipitates An and Bn ……………………………..……...S6

4. TG and DTG curves of precipitates An and Bn ………………………………………………S7

5. Table with crystal data and structure refinement details for 5·12H2O and 6·12H2O …......S8

6. X-ray powder diffractograms of SMPs …………………………………………………………S9

7. UV/Vis diffuse reflectance spectra of SMPs …………………………………………………S10

8. TG and DTG curves of SMPs ..........................................................................................S11

9. Transition and scanning electronic microscopy images of SMPs ....................................S12

10. Confocal laser scanning microscopy images of 3x@SiO2 SMPs ....................................S14

11. Normalized photoemission spectra of SMPs ………….…………………………………....S15

12. Spectroscopic and photophysical parameters of silica materials …………………..….....S16

13. Spectroscopic and photophysical parameters of compounds 1-6 ………………………..S16

14. Photoemission spectra of compounds 1-3 ………..……………………………………...…S17

15. Photoemission spectra of precipitates An and Bn ……………………..………………….S18

16. Scheme of oxidation of 2,3-diphenyl-para-dioxene by 1O2 .............................................S19

17. 1H NMR trace spectra and conversion of 2,3-diphenyl-para-dioxene during photodynamic oxidation in the presence of 1-3 ……………..……………………………………………...S19

18. Normalized photoemission spectra of SMPs ………….…………………………………....S20

19. Nitrogen sorption isotherms…………………..………….…………………………………....S20

S3

Experimental Section

Method. FTIR were recorded on Bruker Vertex 80 in KBr pellets. X-Ray powder diffraction patterns were recorded on a Philips APD 1700 instrument. The thermal properties were studied on a Thermo Microbalance TG 209 F1 Iris (NETZSCH) in the temperature range 25–850 C with a heating rate of 10/min in a helium flow (30 mL/min). Optical diffuse reflectance spectra were measured at room temperature on a Shimadzu UV-Vis-NIR 3101 PC spectrophotometer equipped with an integrating sphere and reproduced in the form of Kubelka–Munk theory. Absorption spectroscopy was conducted using a U-3300 spectrophotometer (Hitachi).

Single-Crystal Diffraction. The single-crystal X-ray diffraction data were collected for 5∙12H2O and 6∙12H2O using the graphite monochromatized MoKα-radiation ( = 0.71073 Å) at 150(2) K on a Bruker APEX DUO diffractometer equipped with a 4K CCD area detector. The φ-scan technique was employed to measure the intensities. Absorption corrections were applied empirically using the SADABS program.[3] The structures were solved by the direct methods of difference Fourier synthesis, and then refined by the full-matrix least squares method using the SHELXTL package.[3] The atomic thermal parameters for non-hydrogen atoms were refined anisotropically. The positions of hydrogen atoms of OH– groups and water molecules were found in a difference Fourier map and refined using the riding model with Uiso(H) = 1.5Ueq(O). More experimental details are given in Table S1. CSD-429897 ([{Mo6Br8}(H2O)2(OH)4]∙12H2O) and CSD-429898 ([{Mo6I8}(H2O)2(OH)4]∙12H2O) contain supplementary crystallographic data for this paper. These data can be obtained free of charge from the Inorganic Crystal Structure Database via http://www.fiz-karlsruhe.de/request_for_deposited_data.html.

References

[1] Bruker AXS Inc. (2004). APEX2 (Version 1.08), SAINT (Version 7.03), SADABS (Version 2.11). Bruker Advanced X-ray Solutions, Madison, WI, USA.

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Figure S1. FTIR-spectra of precipitates A1 and B1.

Figure S2. FTIR-spectra of precipitates A2 and B2.

Figure S3. FTIR-spectra of precipitates A3 and B3.

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Figure S4. FTIR-spectra of 1x@SiO2 SMPs.

Figure S5. FTIR-spectra of 2x@SiO2 SMPs.

Figure S6. FTIR-spectra of 3x@SiO2 SMPs.

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Figure S7. Experimental X-ray powder diffraction patterns of A1, B1 and theoretical diffraction pattern of 4∙12H2O.

Figure S8. Experimental X-ray powder diffraction pattern s of A2, B2 and theoretical diffraction pattern of 5∙12H2O.

Figure S9. Experimental X-ray powder diffraction patterns of A3, B3 and theoretical diffraction pattern of 6∙2H2O.

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Figure S10. TG and DTG curves of A1 (left) and B1 (right).

Figure S11. TG and DTG curves of A2 (left) and B2 (right).

Figure S12. TG and DTG curves of A3 (left) and B3 (right).

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Table S1. Crystal data, data collection and refinement parameters for 5·12H2O and 6·12H2O.

5·12H2O 6·12H2O

Empirical formula Br8H32Mo6O18 H32I8Mo6O18

Formula weight 1535.18 1911.10

Temperature (K) 150(2) 150(2)

Crystal size (mm3) 0.18 0.16 0.14 0.14 0.10 0.10

Crystal system Trigonal Trigonal

Space group R3m R3m

Z 3 3

a (Å) 15.2397(4) 15.7382(11)

c (Å) 11.1438(3) 11.3109(7)

V (Å3) 2241.39(10) 2426.3(3)

Dcalcd. (g cm–3) 3.412 3.924

μ (Mo Kα) (mm–1) 13.198 9.947

θ range (º) 2.39 – 29.99 2.34 – 29.98

h, k, l indices range–21 ≤ h ≤ 14; –21 ≤ k ≤ 21; –12 ≤ l ≤ 15

–22 ≤ h ≤ 8; –8 ≤ k ≤ 21; –15 ≤ l ≤ 5

F(000) 2124 2556

Reflections collected 5856 2389

Unique reflections 810(Rint = 0.0180)

871(Rint = 0.0159)

Observed reflections [I > 2σ(I)] 785 831

Parameters refined 50 50

R[F2 > 2σ(F2)] R1 = 0.0107wR2 = 0.0259

R1 = 0.0166wR2 = 0.0366

R(F2) (all data) R1 = 0.0114wR2 = 0.0260

R1 = 0.0187wR2 = 0.0373

GOOF on F2 1.124 1.163

Δρmax, Δρmin (e Å–3) 0.348, –0.519 0.780, –0.873

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Figure S13. X-ray powder diffraction patterns of neat SMPs and 1x@SiO2 SMPs.

Figure S14. X-ray powder diffraction patterns of neat SMPs and 2x@SiO2 SMPs.

Figure S15. X-ray powder diffraction patterns of neat SiO2 and 3x@SiO2 SMPs.

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Figure S16. UV/Vis diffuse reflectance spectra of neat SMPs and 1x@SiO2 SMPs.

Figure S17. UV/Vis diffuse reflectance spectra of neat SMPs and 2x@SiO2 SMPs.

Figure S18. UV/Vis diffuse reflectance spectra of neat SMPs and 3x@SiO2 SMPs.

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Figure S19. TG curves of neat SMPs and 1x@SiO2 SMPs.

Figure S20. TG curves of neat SMPs and 2x@SiO2 SMPs.

Figure S21. TG curves of neat SMPs and 3x@SiO2 SMPs.

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(A)

(F)(E)(D)

(C)(B)

Figure S22. TEM images of 1x@SiO2 SMPs.(A): x = 0.001; (B): x = 0.01; (C): x = 0.05; (D): x = 0.1; (E): x = 0.5; (F): x = 1.

(A)

(F)(E)(D)

(C)(B)

Figure S23. TEM images of 2x@SiO2 SMPs.(A): x = 0.001; (B): x = 0.01; (C): x = 0.05; (D): x = 0.1; (E): x = 0.5; (F): x = 1.

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(A)

(F)(E)

(D)(C)(B)

(H)(G)

Figure S24. TEM images with Mo L2,3-edge, EF-TEM elemental map of 3x@SiO2 SMPs.(A): x = 0.001; (B): x = 0.005; (C): x = 0.01; (D): x = 0.05; (E): x = 0.1; (F): x = 0.5; (G): x = 1; (H): x = 2.

(A)

(F)(E)(D)

(C)(B)

Figure S25. SEM images of 3x@SiO2 SMPs.(A): x = 0.001; (B): x = 0.01; (C): x = 0.05; (D): x = 0.1; (E): x = 0.5; (F): x = 1.

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(A)

(F)(E)

(D)(C)(B)

(H)(G)

Figure S26. CLSM images of 3x@SiO2 SMPs.(A): x = 0.001; (B): x = 0.005; (C): x = 0.01; (D): x = 0.05; (E): x = 0.1; (F): x = 0.5; (G): x = 1; (H): x = 2.

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550 600 650 700 750 800 850 900 950Wavelength, nm

10.0001@SiO2

10.001@SiO2

10.005@SiO2

10.01@SiO2

10.1@SiO2

10.5@SiO2

Figure S27. Normalized emission spectra of 1x@SiO2 SMPs.

Figure S28. Normalized emission spectra of 2x@SiO2 SMPs.

Figure S29. Normalized emission spectra of 3x@SiO2 SMPs.

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Table S2. The spectroscopic and photophysical parameters of cluster-doped silica materials.

Sample em / nm em em / µs (amplitude)SMPs

10.0001@SiO2 ~ 700 < 0.01 92 (0.04), 14 (0.15), 1.3 (0.81)10.001@SiO2 ~ 710 < 0.01 63 (0.05), 15 (0.12), 1.0 (0.83)10.005@SiO2 ~ 715 < 0.01 63 (0.11), 15 (0.33), 2.5 (0.56)10.01@SiO2 ~ 715 < 0.01 62 (0.07), 15 (0.27), 2.3 (0.66)10.1@SiO2 ~ 720 < 0.01 59 (0.07), 19 (0.30), 5.0 (0.63)10.5@SiO2 ~ 710 < 0.01 62 (0.07), 17 (0.31), 3.1 (0.62)20.0001@SiO2 ~ 695 < 0.01 94 (0.04), 13 (0.14), 1.3 (0.82)20.001@SiO2 ~ 700 < 0.01 93 (0.04), 13 (0.11), 1.5 (0.86)20.005@SiO2 ~ 710 < 0.01 85 (0.05), 13 (0.15), 2.2 (0.80)20.01@SiO2 ~ 715 < 0.01 88 (0.06), 15 (0.15), 2.6 (0.79)20.1@SiO2 ~ 715 < 0.01 47 (0.04), 5.3 (0.15), 0.7 (0.81)20.5@SiO2 ~ 725 < 0.01 468 (0.03), 6.2 (0.14), 1.2 (0.83)21@SiO2 ~ 725 < 0.01 49 (0.04), 6.6 (0.13), 1.3 (0.83)30.0001@SiO2 ~ 700 0.04 135 (0.15), 31 (0.13), 4.0 (0.72)30.001@SiO2 ~ 702 0.08 134 (0.51), 47 (0.21), 5.2 (0.28)30.005@SiO2 ~ 702 0.04 135 (0.50), 48 (0.20), 5.4 (0.30)30.01@SiO2 ~ 702 0.04 134 (0.50), 45 (0.23), 6.6 (0.27)30.1@SiO2 ~ 703 0.02 114 (0.35), 41 (0.25), 5.2 (0.40)30.5@SiO2 ~ 704 0.02 112 (0.20), 29 (0.21), 4.4 (0.59)31@SiO2 ~ 708 0.01 98 (0.14), 34 (0.19), 5.7 (0.67)

SNPs30.001@SiO2 ~ 702 0.12 165 (0.31), 95 (0.53), 21 (0.16)30.005@SiO2 ~ 701 0.06 160 (0.13), 91 (0.26), 11 (0.61)30.01@SiO2 ~ 700 0.03 133 (0.06), 41 (0.04), 2.2 (0.90)30.05@SiO2 ~ 703 < 0.01 107 (0.04), 26 (0.04), 1.9 (0.92)30.1@SiO2 ~ 704 < 0.01 106 ( 0.06), 18 (0.14), 3.4 (0.80)

Table S3. The spectroscopic and photophysical parameters of cluster compounds 1-6.

Sample em / nm em em / µs (amplitude)In Deaerated Acetone

1 ~ 770 0.01 160(0.39), 10(0.61)2 - - -32 ~ 760 0.25 185

In the Solid State15 ~ 765 <0.005 17(0.14), 9.3(0.02), 1.9(0.84)25 ~ 785 < 0.01 19(0.25), 11(0.20), 0.9(0.55)32 ~ 666 0.26 96(0.71), 26(0.29)Precipitate A1 (4∙2H2O) ~ 745 < 0.01 17(0.14), 4.2(0.4), 0.8(0.46)Precipitate A2 (5∙2H2O) ~ 715 0.01 62(0.04), 12(0.13), 2.7(0.83)Precipitate A3 (6∙2H2O) - - -Precipitate B1 (4∙2H2O) ~ 745 < 0.01 20(0.16), 5.6(0.46), 1.2(0.38)Precipitate B2 (5∙6H2O) ~ 705 0.02 66(0.16), 32(0.24), 6.1(0.60)Precipitate B3 (6∙2H2O) - - -

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Figure S30. Emission spectra of cluster complexes 2 and 3 in the solid state.5

Figure S31. Emission spectra of cluster complexes 1, 2 and 3 in an oxygen-free acetone solution.

Table S4. Photoluminescence quantum yields of 3x@SiO2.

Sample em Sample em Sample em

30.0001@SiO2 0.04 30.002@SiO2 0.08 30.03@SiO2 0.0230.0002@SiO2 0.07 30.003@SiO2 0.06 30.04@SiO2 0.0330.0003@SiO2 0.08 30.004@SiO2 0.04 30.05@SiO2 0.0230.0004@SiO2 0.07 30.005@SiO2 0.04 30.06@SiO2 0.0330.0005@SiO2 0.08 30.006@SiO2 0.04 30.07@SiO2 0.0330.0006@SiO2 0.09 30.007@SiO2 0.04 30.08@SiO2 0.0230.0007@SiO2 0.07 30.008@SiO2 0.04 30.09@SiO2 0.0230.0008@SiO2 0.06 30.009@SiO2 0.04 30.1@SiO2 0.0230.0009@SiO2 0.08 30.01@SiO2 0.04 30.5@SiO2 0.0230.001@SiO2 0.08 30.02@SiO2 0.03 31@SiO2 0.01

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Figure S32. Emission spectra of precipitates An (left) and Bn (right).

500 550 600 650 700 750 800 850 900 950Wavelength, nm

A2 B2

Figure S33. Emission spectra of precipitates A2 and B2.

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+O

O Ph

PhO

O PhPh

O

O

1O2

a

a

b

b

2,3-diphenyl-para-dioxene ethylene glycol dibenzoate

Scheme S1. Oxidation of 2,3-diphenyl-para-dioxene by 1O2.

Figure S34. 1H NMR spectra of acetone solutions of 2,3-diphenyl-para-dioxene and the cluster complexes 1-3 after 3 hours of irradiation by light with 400 nm.

Table S5. Conversion of parameters of 2,3-diphenyl-para-dioxene after photoirradiation.

C, M Conversion, %

1 0.008 4

2 0.024 12

3 0.032 16

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550 600 650 700 750 800 850 900 950

Wavelength, nm

30.001@SiO2

30.005@SiO2 30.01@SiO2

30.05@SiO2

30.1@SiO2

Figure S35. Normalized emission spectra of 3x@SiO2 SNPs.

Figure S36. Nitrogen sorption isotherms at 77 K: a) 30.001@SiO2 MPs; b) 30.001@SiO2 NPs