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S1 Supporting Information Comparative Study of Optical Properties and X-ray Induced Luminescence of Octahedral Molybdenum and Tungsten Cluster Complexes Darya V. Evtushok, a Anatoly R. Melnikov, b,c Natalya A. Vorotnikova, a Yuri A. Vorotnikov, a Alexey A. Ryadun, a Natalia V. Kuratieva, a,c Konstantin V. Kozyr, d Natalia R. Obedinskaya, d Evgeniy I. Kretov, d Igor N. Novozhilov, a Yuri V. Mironov, a,c Dmitri V. Stass, b,c Olga A. Efremova,* e Michael A. Shestopalov** a,c,f a Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, Russian Federation. b Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya st., Novosibirsk, 630090, Russian Federation. c Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russian Federation d Meshalkin Siberian Federal Biomedical Research Center, 15 Rechkunovskaya st., 630055 Novosibirsk, Russian Federation e School of Mathematics and Physical Sciences, University of Hull, Cottingham Road, HU6 7RX, Hull, UK. f Research Institute of Experimental and Clinical Medicine, 2 Timakova Str., 630060 Novosibirsk, Russian Federation. *Corresponding Authors: *Olga A. Efremova Tel: +441482465417, Fax: +441482466410 e-mail: [email protected]. **Michael A. Shestopalov Tel. +7-383-330-92-53, Fax +7-383-330-94-89 e-mail: [email protected] Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2017

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Page 1: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

S1

Supporting Information

Comparative Study of Optical Properties and X-ray Induced Luminescence of Octahedral Molybdenum and Tungsten Cluster Complexes

Darya V. Evtushok,a Anatoly R. Melnikov,b,c Natalya A. Vorotnikova,a Yuri A. Vorotnikov,a Alexey A. Ryadun,a Natalia V. Kuratieva,a,c Konstantin V. Kozyr,d Natalia R. Obedinskaya,d Evgeniy I. Kretov,d Igor N. Novozhilov,a Yuri V. Mironov,a,c Dmitri V. Stass,b,c Olga A. Efremova,*e Michael A. Shestopalov**a,c,f

aNikolaev Institute of Inorganic Chemistry SB RAS, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, Russian Federation.bVoevodsky Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya st., Novosibirsk, 630090, Russian Federation.cNovosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russian FederationdMeshalkin Siberian Federal Biomedical Research Center, 15 Rechkunovskaya st., 630055 Novosibirsk, Russian FederationeSchool of Mathematics and Physical Sciences, University of Hull, Cottingham Road, HU6 7RX, Hull, UK.fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., 630060 Novosibirsk, Russian Federation.

*Corresponding Authors:*Olga A. EfremovaTel: +441482465417, Fax: +441482466410e-mail: [email protected].

**Michael A. ShestopalovTel. +7-383-330-92-53, Fax +7-383-330-94-89e-mail: [email protected]

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

Page 2: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

S2

ContentCrystallographic data for compounds 2-4 and selected interatomic distances for 2-4, 6-8.........................3

FTIR-spectra of 2-4 and 1H NMR spectrum of 3............................................................................................4

3D framework of hydrogen bonding in 4·12H2O ..........................................................................................5

X-ray powder diffraction patterns and TG and DTG curves of 4·6H2O .........................................................6

The emission spectra of 1-3..........................................................................................................................7

The samples for X-ray attenuation and the dependence of radiodensity of 1, 2, 5 and 6 in solid state vs. concentration ...............................................................................................................................................8

Study of electrochemical properties of compounds 1-3 ..............................................................................9

The samples for X-Ray induced photoluminescence measurements and the estimated χX values ...........10

X-Ray induced Luminescence measurements –additional information .....................................................11

Spectral sensitivity calibration .................................................................................................................11

Corrected non-normalised X Ray induced emission spectra of compounds 1-8. ....................................12

X-Ray bleaching compounds 2 and 6 .......................................................................................................13

Consistency for independent full cycles of sample preparation and measurement of X-Ray induced luminescence ...........................................................................................................................................15

Photo-degradation studies .........................................................................................................................17

Page 3: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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Crystallographic data for compounds 2-4 and selected interatomic distances (Å) for compounds 2-7Table 1S. Crystallographic data for compounds 2-4.

Table 2S. Selected interatomic distances (Å) for 2-4, 6-8.

2·CH2Cl2 3·(CH3)2CO·1.5(C2H5)2O 4·12H2O

Empirical formula C33H74Cl2I8N8O18W6 C83H135I8N2O20.5S6W6 H32I8O18W6

Formula weight 3060.20 3799.59 2438.56Crystal system Monoclinic Triclinic TriclinicSpace group P 21/n P1 P1

a, Å 14.4535(6) 13.412(2) 9.5082(2)b, Å 11.3287(4) 16.210(2) 9.8579(2)c, Å 21.6572(7) 27.147(3) 9.9671(2)ɑ, º 89.271(3) 74.110(1)β, º 95.633(1) 79.227(3) 67.878(1)γ, º 77.959(3) 88.438(1)

V, Å3 3529.0(2) 5668(1) 829.36(3)Z 2 2 1

Calc. density, g cm–3 2.880 2.226 4.882μ, mm–1 13.373 8.411 28.220

Crystal size, mm3 0.30 × 0.25 × 0.25 0.28 × 0.10 × 0.06 0.20 × 0.10 × 0.08Θ range, º 2.29 – 26.37 0.76 – 26.37 2.30 – 30.67

Index ranges–15 ≤ h ≤ 18–14 ≤ k ≤ 14–27 ≤ l ≤ 15

–16 ≤ h ≤ 16–20 ≤ k ≤ 17–33 ≤ l ≤ 33

–13 ≤ h ≤ 8–14 ≤ k ≤ 14–14 ≤ l ≤ 10

Reflections collected/ independent (Rint)

27204 / 6889(0.0352)

44791 / 23089(0.0221)

10599 / 5093(0.0302)

Completeness, % 96.4 99.6 99.4Data / restraints /

parameters6889 / 35 / 396 23089 / 49 / 1150 5093 / 0 / 165

Goodness-of-fit 1.029 1.063 1.079R1, wR2 (I>2σ(I)) 0.0310, 0.0760 0.0381, 0.0891 0.0229, 0.0575R1, wR2 (all data) 0.0399, 0.0801 0.0505, 0.0943 0.0245, 0.0582

Δρmax, Δρmin, eÅ–3 1.804, –1.240 2.603, –1.835 1.724, –2.470

2·CH2Cl2 3·(CH3)2CO·1.5(C2H5)2O 4·12H2O

W–W (Å) 2.6549(4)–2.6656(4) 2.622(9)–2.724(8) 2.6538(2)–2.6660(2)W–I (Å) 2.7791(5)–2.8064(5) 2.722(6)–2.816(1) 2.8181(4)–2.8431(3)W–O (Å) 2.144(5)–2.153(5) 2.123(6)–2.134(5) 2.087(3)–2.104(4)

6·3(CH3)2CO 7·(CH3)2CO·1.5H2O 8·12H2OMo-Mo 2.6664(9)–2.6776(9) 2.6604(8)–2.6718(7) 2.6594(5)–2.6797(5)

Mo-I 2.7667(8)–2.7857(8) 2.7550(6)–2.7871(7) 2.7643(4)–2.7987(4)Mo-O 2.133(6)–2.154(6) 2.125(4)–2.146(4) 2.143(3)

Page 4: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

S4

FTIR-spectra of 2-4 and 1H NMR spectrum of 3

3000 2500 2000 1500 1000 500Wavenumber, cm-1

2

3

4·6H2O

νas (N

O2 )

νs (N

O2 )

ν(NO

)

νas (SO

2 )

νs (SO

2 )

ν(SO)

Figure 1S. FTIR-spectra of 2-4.

Figure 2S. 1H NMR spectrum of 3 in acetone-d6.

Page 5: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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3D framework of hydrogen bonding in 4·12H2O

Figure 3S. 3D framework of hydrogen bonding between OH–/H2O ligands and water of crystallisation in 4·12H2O.

Page 6: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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X-ray powder diffraction patterns and TG and DTG curves of 4·6H2O

5 10 15 20 25 30 35 402Θ, o

4·6H2O 4·12H2O theor

Figure 4S. Experimental X-ray powder diffraction patterns of 4·6H2O and theoretical diffraction pattern of 4·12H2O.

100 200 300 400 500 600 700 800

50

60

70

80

90

100

–2H2O

t = 210 oC, mass loss 6.2%

Temperature, oC

–6H2O

t = 130 oC, mass loss 4.6%

-7

-6

-5

-4

-3

-2

-1

0

1

2TG/% DTG/(%/min)

Figure 5S. TG and DTG curves of 4·6H2O.

Page 7: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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The emission spectra of 1-3

500 600 700 800

1 2 3 4·6H2O

Wavelength, nm500 600 700 800

1 2 3

Wavelength, nm

Figure 6S. Normalised raw emission spectra of 1-4 in the solid state (left) and emission spectra of 1-3 in argon-saturated CH3CN solutions.

Page 8: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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The samples for X-ray attenuation and the dependence of radiodensity of 1, 2, 5 and 6 in solid state vs. concentration

Figure 7S. 1, 2, 5 and 6 in DMSO solutions (left) and in the mixture with α-lactose monohydrate (right)

0 1x10-5 2x10-5 3x10-5 4x10-5 5x10-5 6x10-50

500

1000

1500

2000

2500

3000

3500

Concentration, mol/g

Rad

iden

sity

, HU

1 2 5 6

Figure 8S. The dependence of radiodensity of 1, 2, 5 and 6 in solid state in Hounsfield unit scale vs. concentration.

Page 9: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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Study of electrochemical properties of compounds 1-3

Cyclic voltammetry (CV) was performed using a Metrohm 797 VA Computrace instrument with a glassy carbon electrode as the working electrode and a saturated silver / silver chloride (Ag/AgCl) in 3.5 M KCl as a reference electrode. The potentials were related to the standard platinum electrode. A 0.10 M solution of tetra-n-butylammonium tetrafluoroborate (nBu4NBF4) in dimethyl sulfoxide (DMSO) was used as the electrolyte. Solutions of the samples in the electrolyte (1-2 mM) were degassed by purging with argon prior to CV measurements. Compounds were investigated voltammetrically within the potential window from –2V to 1.8V at 25 °C. The formal half-wave potentials (E1/2) were calculated as the midpoint between the anodic and cathodic peak. Table 3S summarises the oxidation and reduction potentials, as well as electrochemical energy gap calculated as a difference between onsets of oxidation and reduction waves. CV data of compounds 1-3 demonstrate reversible oxidation in the positive region of thepotentials and the irreversible reduction in the negative region.

Table 3S. Formal half-wave potentials (E1/2) onset of oxidation (Eoxonset) and reduction (Ered

onset) potentials (calculated electrochemical energy gaps) of compounds 1-3 in DMSO vs. saturated Ag/AgCl couple. The scan rate was 0.05 V·s−1.

Е1/2, VCompound

[{W6I8}L6]1-/2- [{W6I8}L6]2-/3-Eox

onset, V Eredonset, V

Electrochemical

energy gap, eV

1 1.12 -1.55 1.06 -1.29 2.35

2 1.36 -1.65 1.28 -1.34 2.62

3 1.48 -1.51 1.37 -1.23 2.60

Page 10: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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The samples for X-Ray induced photoluminescence measurements and the estimated χX values

Figure 9S. Photo-images of naked thin strips of powdered samples of compounds 1-8 for X-Ray induced photoluminescence measurements.

Table 4S. The estimated χX values for the eight complexes

Complex λem, nm Integration range, nm χX Value1 669 400 – 673 1.2·104

2 676 450 – 678 1.2·102

3 645 400 – 648 6.1·103

4·6H2O 750 500 – 760 2.0·101

5 780 550 – 797 7.8·102

6 668 500 – 668 4.2·102

7 670 500 – 669 3.0·103

8·2H2O - 500 – 670 < 1

Page 11: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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X-Ray induced Luminescence measurements –additional informationSpectral sensitivity calibration: A sputtered MgO diffuser was prepared and installed in place of the sample. X-ray tube was substituted for an incandescent lamp with precisely known temperature of the filament (2850 K at the working point, TRSh2850-3000 lamp provided as an accessory to commercial SDL-2 spectrophotometer by LOMO Photonics, St. Petersburg, Russia), and the emission spectrum was recorded. The black body emission curve for the given temperature was calculated, and the ratio of the two curves was taken, which was used as the calibration curve. This procedure was repeated for several settings of the slits on the detection channel monochromator, as the detection system showed a rather narrow dip in the spectral sensitivity curve, whose appearance in the experimental spectrum slightly varied with opening the slits of the monochromator. All spectra presented here and in the main text were recorded with 2.2 mm/2.2 mm slits, and the calibration curve taken at these slits was used for correction. Note that while the spectra were taken/calculated up to 1000 nm, the calibration curve has been truncated at 800 nm, where the correction factor already reaches 36, nominally shooting to 200 at 850 nm and to 880 at 900 nm. Multiplication of the experimental curves by such huge correction factors is exceptionally prone to noise and minor deviations of baseline correction. This was the reason for choosing 800 nm, as the practical red boundary of all spectra analysed in this work.

Page 12: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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Figure 10S. Corrected non-normalised X Ray induced emission spectra of compounds 1-8.

Page 13: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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X-Ray bleaching compounds 2 and 6

0 100 200 300 400 500 600 700 800 900 10000

1

2

3

4

5

6

7 y = 4.8 - 0.0002x

I, a.

u.

t, s(a)

0 100 200 300 400 500 600 700 800 900 10000

10

20

30 y = 21.3 - 0.002x

I, a.

u.

t, s

(b)

Figure 11S. Typical kinetics of the decay of emission for samples of compound 2 at 660 nm (a) and 6 at 600 nm (b) under steady-state irradiation.

Page 14: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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450 500 550 600 650 700 7500

4

8

12

16

20

I, a.

u.

, nm

0 min 40 min 100 min 140 min

(a)

500 550 600 650 700 750 8000

30

60

90

120

150 0 min 60 min 100 min 140 min next day

I, a.

u.

, nm

(b)

Figure 12S. Corrected emission spectra of 2 (a) and 6 (b) after given times of X-ray exposer. The spectra marked as “next day” were recorded to demonstrate that the bleaching occurs only under X-Ray irradiation, i.e. leaving the samples overnight without X-Ray irradiation does not cause any degradation.

Page 15: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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Consistency for independent full cycles of sample preparation and measurement of X-Ray induced luminescence

(a)

(b)

Figure 13S. Two independent complete cycles of preparation and measurements of X-ray induced luminescence for samples of compounds 3 (a) and 7 (b). Left: original spectra; Right: corrected and normalised spectra

Page 16: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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500 550 600 650 700 750 800 850Wavelength, nm

1 Photoluminescence 1 XEOL

500 550 600 650 700 750 800 850Wavelength, nm

3 Photoluminescence 3 XEOL

550 600 650 700 750 800 850Wavelength, nm

5 Photoluminescence 5 XEOL

550 600 650 700 750 800 850Wavelength, nm

6 Photoluminescence 6 XEOL

Figure 14S. Comparison of photoluminescene and X-ray induced luminescence spectra for 1, 3, 5 and 6.

Page 17: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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Photo-degradation studies

Figure 15S. Color of crystals of 2 before photoirradiation (a), after 2 min (b) and after 10 min of photoirradiation (c).

200 250 300 350 400 450 5000.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Wavelength, nm

Abso

rban

ce

0 s 60 s 120 s 300 s 600 s 1200 s

Figure 16S. UV-Vis spectra of 5 after photoirradiation.

250 300 350 400 450 500 550 600 6500.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Abso

rptio

n

Wavelength, nm

After 510 s of irrdaiation, Ar atmosphere After 25 min After 18 h

Figure 17S. UV-vis spectrum of 2 in acetonitrile in argon atmosphere after 510 s of photoirradiation and the evolution of the spectrum after 25 min in darkness and after 18 h in darkness.

a b c

Page 18: Supporting Information Complexes Luminescence of ...Hull, UK. fResearch Institute of Experimental and Clinical Medicine, 2 Timakova Str., ... 3D framework of hydrogen bonding in 4·12H2O

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250 300 350 400 450 5000.0

0.1

0.2

0.3

0.4

0.5 Fresh solution 18 h

Wavelength, nm

Abso

rban

ce

Figure 18S. UV-Vis spectra of a freshly prepared in acetonitrile solution of 2 and of the same solution after 18 h in darkness in ambient atmosphere.

Figure 19S. Theoretical and experimental peaks of [W6O19]2− and (Bu4N)[W6O19]− in ESI-MS