View
2
Download
0
Category
Preview:
Citation preview
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.
alexander.sorokin@ircelyon.univ-lyon1.fr, pavel.afanasiev@ircelyon.univ-lyon1.fr
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
3
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4
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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
5
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
6
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
8
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
9
[(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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
10
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
11
-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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
12
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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
13
Supplementary Figure S9. Spin density at the same surface isovalue 0.02 for the initial
FePcCl (top) and for the oxo-complex (bottom).
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
14
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
15
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
16
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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
17
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
18
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Recommended