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1 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. Koifman b 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 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2012

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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  • 1

    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

    Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

  • 2

    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

    862.2 963.2

    +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 7118E / eV

    Inte

    nsity

    / a.

    u.

    TotalXYZ

    0

    1

    2

    3

    4

    5

    6

    7

    7110 7112 7114 7116 7118E /eV

    Inte

    nsity

    / a.

    u.

    TotalXYZ

    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 7075E / eV

    Em

    issi

    on n

    tens

    ity /

    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

    Abso

    rptio

    n

    initial

    oxo-complex

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    0

    2

    4

    6

    8

    0 1 2 3 4R / Ǻ

    FT m

    odul

    e

    Initial

    oxo-complex

    0

    4

    8

    12

    0 1 2 3 4R / Ǻ

    FT m

    odul

    e

    oxo-complexInitial

    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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