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Page 1: Supplementary Information for1 Supplementary Information for Generation and characterization of high-valent iron oxo phthalocyanine Pavel Afanasiev,*a Evgeny V. Kudrik,a,b Florian

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Supplementary Information for

Generation and characterization of high-valent iron oxo phthalocyanine

Pavel Afanasiev,*a Evgeny V. Kudrik,a,b Florian Albrieux,c Valérie Briois,d Oskar I.

Koifmanb and Alexander B. Sorokin*a

a Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), CNRS,

UMR 5256, Université Lyon 1, 2, av. A. Einstein, 69626 Villeurbanne, France.

[email protected], [email protected]

b Institute of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and

Technology, 7, av. F. Engels, 153000, Ivanovo, Russia.

c Université Lyon 1, UMR 5246, Centre Commun de Spectrométrie de Masse, 43 bd du 11

Novembre 1918, 69622 Villeurbanne cedex, France.

d Synchrotron Soleil, L’orme des merisiers, St-Aubin,

91192 Gif-sur-Yvette, France.

This PDF file includes:

Materials and Methods

Supplementary References

Supplementary Figures S1 to S13

Supplementary Table S1

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Materials

m-Chloroperbenzoic acid (m-CPBA, 75 % content) was purchased from Sigma-Aldrich.

Labeled water H218O (95.4 atom. % 18O, 0.6 atom % 17O, 4.0 atom % 16O) was obtained

from Euriso-top. Tetra-tert-butylphthalocyaninatoiron(II) was synthesised and purified

according to published protocol (S1). The complex (100 mg) was dissolved in 40 mL of

dichloromethane. After addition of HCl solution (1 mL) the resulting mixture was stirred at

room temperature for 6 h. The solvent was evaporated and the solid product was dried at

room temperature in vacuum for 6 h.

The iron(IV) oxo complex, (PctBu4)Fe=O(Cl), was prepared from (PctBu4)FeCl (2·10 M-3 –

10-6 M) and meta-chloroperbenzoic acid (3 – 10 equivalents) in acetone at -60°C (low

complex concentration) or at -75 °C (high complex concentration).

Equipment and Methods

The mass spectra were recorded in a positive ion mode on a hybrid quadrupole time-of-

flight mass spectrometer (MicroTOFQ-II Bruker Daltonics, Bremen) with a Cold Spray

Ionization (CSI) ion source. CSI allows to keep intact labile compound in the gas phase.

The CSI temperatures conditions for this analysis were -20°C for the spray gas and 2°C for

the dry gas. The gas flow of dry gas was 6 L/min and spray gas pressure was 0,5 bar, the

capillary voltage is 4,5kV. The solutions were infused at 200 µL/h in acetone as solvent.

The mass range of the analysis is 50-1000m/z and the calibration was done with sodium

formate. The UV-vis spectra of solutions were obtained with Agilent 8453 diode-array

spectrophotometer. Low temperature UV-vis studies were carried out using liquid nitrogen

cooled cryostat and a C Technologies immersion probe (5 mm path length) and fiber-optic

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cable. EPR spectra were recorded on a Bruker Elexsys e500; conditions : 25°C, microwave

frequency 9.415 GHz, power 0.4 mW, modulation 1.0 mT/100 kHz.

The EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray absorption

near-edge structure) spectra were recorded on the SAMBA beamline, at the SOLEIL

synchrotron (Gif-sur-Yvette, France), operating at 300 mA, 2.75 GeV). Spectra were

collected in transmission mode at the Fe K-edge with a sagittal focusing double crystal

Si(220) and focusing mirrors graded at 5 mrad to remove the harmonics. The beam spot

was de-focused to prevent beam damage to the sample. To compare the pre-edge energy,

metallic Fe foil reference was applied. The first inflection point of metallic Fe was

observed at 7111.6 eV. The data were treated with FEFF (S2) and VIPER (S3) programs.

Then the edge background was extracted using Bayesian smoothing with variable number

of knots. The spectra were simulated based on the DFT-optimized structures, using full

multiple scattering in the range 4.5 Ǻ.

X-ray scattering and X-ray emission spectra were measured at beamline ID 26 at the

European synchrotron Radiation Facility (ESRF), Grenoble, France. The electron energy

was 6.0 GeV, and the ring current varied from 50 to 90 mA. Two u35 undulators were used

to perform the measurements. To detect the (resonant) inelastic X-ray scattering the sample

pellet (powder or frozen solution) was aligned to the X-ray beam at an angle of 45°. The

incident X-ray energy was selected by a pair of Si crystals cut in (2 2 0) orientation. The

beam was focused in a small spot (350 μm × 60 μm) on the sample. The scattered X-rays

were monochromatized by the (5 3 1) Bragg planes of a spherical bent Si crystal and

focussed on an avalanche photodiode (APD). When scanning the energy of the scattered X-

rays, the APD detector and the spherical bent Si crystal were moved concertedly in order to

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keep the beam spot on the sample, the bent crystal and the detector on a Rowland circle. A

He bag was fixed between sample, analyzer crystal and detector in order to minimize the

absorption of the X-rays by air.

In most experiments, instead of measuring the full RIXS plane, the emission energy

was fixed either at the maximum of the Kβ1,3 or the Kβ′ emission line and only the incident

energy was scanned. To determine the position of the main and satellite emission line, a Kβ

emission spectrum (XES) was recorded first under non-resonant conditions, with an

incident energy above the Fe K-edge at 7160 eV.

The reaction products were identified by GC-MS method (Hewlett Packard 5973/6890

system ; electron impact ionization at 70 eV, He carrier gas, 30m x 0.25 mm HP-INNOWax

capillary column, polyethylene glycol (0.25 µm coating) or DB-5MS 50 m capillary

column (0.250 mm x 0.25 m).

References

S1. J. Metz, O. Schneider and M. Hanack, Inorg. Chem., 1984, 23, 1065-1071.

S2. A. L. Ankudinov, C. E. Bouldin, J. J. Rehr, J. Sims and H. Hung, Phys. Rev. B,

2002, 65, 104-107.

S3. K. V. Klementiev, J. Synchrotron Rad.,2001, 8, 270-272.

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Supplementary Figure S1. (a) Positive ESI-MS spectrum of PctBu4FeCl. (b) Experimental

isotope distribution pattern of the [PctBu4Fe]+ cluster peak. (c) Calculated isotope

distribution pattern for C48H48N8Fe1.

a

b

c

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Supplementary Figure S2. (a) Positive ESI-MS spectrum of PctBu4FeCl. (b) Experimental

isotope distribution pattern of the molecular cluster peak. (c) Calculated isotope distribution

pattern for C48H48N8Fe1Cl1.

a

b

c

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792.3 808.3

827.2

843.2

862.2963.2

+MS, 1.1-1.2min #(64-69)

0

5

10

15

20

25

Intens.[%]

800 820 840 860 880 900 920 940 960 m/z

963.2

964.2

965.2

966.2

+MS, 1.1-1.2min #(64-69)

0.0

0.5

1.0

1.5

Intens.[%]

958 960 962 964 966 968 970 972 974 m/z

961.3 962.3

963.3

964.3

965.3

966.3

967.3

QTOF_120203_16_AS-815-O2.d: C55H52N8O3Fe1Cl1, M ,963.32

0

20

40

60

80

100

Intens.[%]

958 960 962 964 966 968 970 972 974 m/z

Supplementary Figure S3. (a) Detection of (PctBu4)FeIII-OOC(O)C6H4Cl peroxocomplex.

(b) Experimental isotope distribution pattern of the [PctBu4Fe-OOC(O)C6H4Cl]+ cluster

peak. (c) Calculated isotope distribution pattern for C55H52N8O3Fe1Cl1.

a

b

c

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792.3808.3

827.2

843.2

858.3 963.2

QTOF_120203_16_AS-815-O2.d: +MS, 1.3min #75

0

5

10

15

20

25

Intens.[%]

800 820 840 860 880 900 920 940 960 m/z

Supplementary Figure S4. (a) Positive ESI-MS spectrum of [(PctBu4)FeIV=O(Cl)]+. (b)

Experimental isotope distribution pattern of the molecular cluster peak of

a

b

c

d

e

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[(PctBu4)FeIV=O]+. (c) Calculated isotope distribution pattern for C48H48N8Fe1O1. (d)

Experimental isotope distribution pattern of the molecular cluster peak of

[(PctBu4)FeIV=O(Cl)]+. (e) Calculated isotope distribution pattern for C48H48N8Fe1O1Cl1.

Supplementary Figure S5. Molecular peak cluster of [(PctBu4)FeIV=O]+ obtained with m-

CPBA in the standard conditions (a), in the presence of 20 µL of H218O per 1 mL of 10-6 M

complex solution (b) and in the presence of 40 µL of H218O per 1 mL of 10-6 M complex

solution (c).

b

a

c

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Supplementary Figure S6. Molecular peak cluster of of [(PctBu4)FeIV=O(Cl)]+ obtained

with m-CPBA in the standard conditions (a), in the presence of 20 µL of H218O per 1 mL of

10-6 M complex solution (b) and in the presence of 40 µL of H218O per 1 mL of 10-6 M

complex solution (c).

a

b

c

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-0.6

-0.2

0.2

0.6

1

2500 3000 3500 4000 4500

H

I /

a. u

.

Supplementary Figure S7. EPR spectrum after addition of m-CPBA to the (PctBu4)FeCl

solution in acetone at -75°C. Recorded at 120 K, microwave frequency 9.392 GHz, power

1.6 mW, modulation 1.0 mT/100 kHz.

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0

2

4

6

8

10

12

14

7110 7112 7114 7116 7118

E / eV

Inte

nsi

ty /

a.u

.

Total

X

Y

Z

0

1

2

3

4

5

6

7

7110 7112 7114 7116 7118

E /eV

Inte

nsity

/ a.

u.

Total

X

Y

Z

Supplementary Figure S8. Time dependent DFT- calculated pre-edge feature of FePcCl

(top) and oxo-complex (bottom) . Shift of 183.1 eV have been applied to calculated spectra

Note that for the spectrum (b) Z – component represents the totality of pre-edge intensity

whereas for the initial compound X- and Y –components are important. Line broadening of

0.2 eV was chosen significantly lower than in the experiment (ca 1 eV), to reveal better the

composite structure of pre-edge.

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Supplementary Figure S9. Spin density at the same surface isovalue 0.02 for the initial

FePcCl (top) and for the oxo-complex (bottom).

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Supplementary Figure S10 Frontier orbitals of the oxo complex [(PctBu4)FeIV=O(Cl)].

Isosurfaces are generated by Gabedit software.

HOMO ; -0.2050

LUMO , LUMO+1; -0.1484

HOMO-1, HOMO-2 ; -0.2064

LUMO + 2 ; -0.1170

LUMO + 3 ; -0.1111

HOMO-3 ; -0.2266

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0

20

40

60

7025 7035 7045 7055 7065 7075

E / eV

Em

issi

on

nte

nsi

ty /

a.u

. initial

oxo-complex

Supplementary Figure S11. Pre-edge and main jump region of normalized XANES

spectra of the initial (PctBu4)FeCl and of the oxo complex (PctBu4)Fe=O(Cl) measured at

77 K in frozen acetone solution.

Supplementary Figure S12. X-ray emission Kβ spectra of the initial (PctBu4)FeCl and the

oxo complex (PctBu4)Fe=O(Cl).

0

0.1

0.2

0.3

0.4

7107 7112 7117 7122

E / eV

Abs

orpt

ion

initial

oxo-complex

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0

2

4

6

8

0 1 2 3 4

R / Ǻ

FT

mo

dule

Initial

oxo-complex

0

4

8

12

0 1 2 3 4

R / Ǻ

FT

mo

du

le

oxo-complex

Initial

Supplementary Figure S13 Experimental (top) and theory (bottom) FT EXAFS spectra

for the monomeric iron phthalcocyanne chloride and its oxo-complex. Theory predicts

damping of the first shell signal and its slight shift towards higher distances, as well as

decrease of the second shell signal intensity.

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Supplementary Table S1 XYZ coordinates of atoms in the optimized structure of the non substituted FePcCl oxo-complex. H 1.237185 -7.510599 0.021234 H -1.237094 -7.510631 0.021768 C 0.702106 -6.559829 0.015370 C -0.702051 -6.559852 0.015704 H 2.520834 -5.357374 0.007977 C 1.430210 -5.357685 0.007622 C -1.430183 -5.357718 0.008344 H -2.520808 -5.357426 0.009160 C 0.704153 -4.168703 -0.001652 H 5.357746 -2.520699 0.002770 C -0.704153 -4.168721 -0.001296 H 7.510912 -1.237007 0.012493 N 2.390438 -2.390251 -0.014550 C 1.115425 -2.762170 -0.011814 C 5.357999 -1.430072 0.002431 C 6.560110 -0.701976 0.008208 C -1.115444 -2.762193 -0.011422 C 4.168935 -0.704084 -0.005019 C 2.762516 -1.115199 -0.012866 N -0.000020 -1.956944 -0.011711 N -2.390459 -2.390265 -0.013435 C 6.560117 0.702195 0.008593 H 7.510918 1.237232 0.013140 H -5.357741 -2.520659 0.007764 N 1.957137 0.000143 -0.011458 C 4.168945 0.704338 -0.004633 O 0.000465 0.000271 -1.785429 C -2.762496 -1.115214 -0.011579 C 5.358014 1.430309 0.003179 Fe 0.000013 0.000094 -0.111488 C -5.357970 -1.430034 0.006951 C 2.762524 1.115466 -0.012397 Cl -0.000075 -0.000227 2.336299 C -4.168905 -0.704069 -0.002238 N -1.957069 0.000125 -0.011394 H 5.357789 2.520935 0.004098 H -7.510864 -1.236911 0.019675 C -6.560056 -0.701908 0.013993 N 2.390465 2.390548 -0.013678 N 0.000008 1.957233 -0.011394 C -2.762468 1.115467 -0.011741 C -4.168885 0.704355 -0.002403 C 1.115470 2.762491 -0.011158 C -6.560035 0.702265 0.013831 C -5.357930 1.430357 0.006652 C -1.115436 2.762505 -0.011526 N -2.390432 2.390543 -0.013770 H -7.510820 1.237322 0.019434 C 0.704175 4.169025 -0.001166 H -5.357672 2.520982 0.007229

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C -0.704139 4.169028 -0.001478 H 2.520845 5.357696 0.009270 C 1.430221 5.358012 0.008417 C -1.430183 5.358020 0.007707 H -2.520807 5.357711 0.008069 C 0.702100 6.560149 0.015705 C -0.702062 6.560152 0.015351 H 1.237140 7.510940 0.021755 H -1.237109 7.510942 0.021110

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