S1
Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative
Dehydrogenation of Propane at Low Temperature
Zhanyong Li†1, Aaron W. Peters†1, Varinia Bernales†2, Manuel A. Ortuño†2, Neil M.
Schweitzer3, Matthew R. DeStefano1, Leighanne C. Gallington4, Ana E. Platero-Prats4,
Karena W. Chapman4, Christopher J. Cramer2*, Laura Gagliardi2*, Joseph T. Hupp*1 and
Omar K. Farha*1,5
1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United
States
2. Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota,
Minneapolis, Minnesota 55455, USA
3. Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road,
Evanston, Illinois 60208, United States
4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439-
4858, United States
5. Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
†These authors contribute equally to this work (the first two, the experiments, the second two,
the theory).
Corresponding authors: C.J.C. ([email protected]), L.G. ([email protected]), J.T.H. (j-
[email protected]) or O.K.F ([email protected]).
S2
Table of Contents
Materials ................................................................................................................................. S4
Physical methods and measurements ................................................................................... S4
Gas-phase catalysis ................................................................................................................. S2
Syntheses ................................................................................................................................. S3
Characterization ..................................................................................................................... S3
Computational modeling ..................................................................................................... S15
List of Figures
Figure S1. Structural representation of the used cobalt precursor, bis(N,N′-di-isopropyl-
acetamidinato)Co(II), Co(MeC(Ni-Pr)2)2. ................................................................................ S4
Figure S2. Characterization of Co-AIM+NU-1000 before catalysis: a, SEM-EDS line scan of
Co (red) and Zr (blue) and a baseline (green) b. powder X-ray diffraction pattern (black) as
compared to that of NU-1000 (blue). c, N2 isotherm of Co-AIM (blue) as compared to the
parent MOF, NU-1000 (red). D, XPS scan of the as-synthesized Co-AIM in the Co 2p region.
.................................................................................................................................................. S5
Figure S3. Characterization of Co-SIM+NU-1000 before catalysis: a, SEM image b. powder
X-ray diffraction pattern (green) as compared to that of NU-1000 (blue). c, N2 isotherm
(green) compared to that of the parent MOF, NU-1000 (blue). d, XPS spectrum of the as-
synthesized Co-SIM+NU-1000 in the Co 2p region. ............................................................... S5
Figure S4. DFT calculated pore-size distributions of Co-AIM and Co-SIM+NU-1000 before
and after propane ODH catalysis. ............................................................................................ S6
Figure S5. DRIFTS spectra of as-synthesized Co-SIM and Co-AIM+NU-1000 as compared
to the parent MOF, NU-1000. .................................................................................................. S6
Figure S6. TGA diagram of NU-1000, Co-SIM and Co-AIM+NU-1000 before catalysis
under a flow of N2. ................................................................................................................... S6
Figure S7. Temperature programmed oxidation data of Co-AIM+NU-1000 and Co-SIM+NU-
1000 as compared to the parent MOF NU-1000. ..................................................................... S7
Figure S8. Oxidative dehydrogenation of propane catalyzed by Co-AIM+NU-1000 (a) and
Co-SIM+NU-1000 (b)at 200 °C where the TOF is determined to be 0.36±0.06 and 0.27±0.09
h−1 for these two materials, respectively. ................................................................................. S7
Figure S9. Characterization of Co-ZrO2 after calcination at 600 °C in air. (a). SEM image (b).
Corresponding elemental map of Co, and (c) elemental map of Zr. (d) N2 isotherms of Co-
ZrO2 at 77 K. ............................................................................................................................ S8
Figure S10. The determination of the TOF for the propane ODH process catalyzed by Co-
ZrO2 at 230 °C. ......................................................................................................................... S8
Figure S11. Delplots for Co-SIM+NU-1000 (a) and Co-AIM+NU-1000 (b) for the oxidative
dehydrogenation of propane. .................................................................................................... S9
Figure S12. XANES spectra for Co-SIM, Co-AIM+NU-1000 before and after activation,
along with the data for cobalt reference samples. .................................................................. S10
Figure S13. Experimental (blue) and fit (orange) data for the Co-ZrO2 before activation in O2
at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d, imaginary part of
R-space. .................................................................................................................................. S10
S3
Figure S14. Experimental (blue) and fit (orange) data for the Co-AIM+NU-1000 before
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space. ..................................................................................................... S11
Figure S15. Experimental (blue) and fit (orange) data for the Co-SIM+NU-1000 before
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space. ..................................................................................................... S11
Figure S16. Experimental (blue) and fit (orange) data for the Co-AIM+NU-1000 after
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space. ..................................................................................................... S12
Figure S17. Experimental (blue) and fit (orange) data for the Co-SIM+NU-1000 after
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space. ..................................................................................................... S12
Figure S18. Characterization of Co-AIM+NU-1000 after propane ODH catalysis: a, SEM-
EDS line scan of Co (green) and Zr (blue) and a baseline (red) b. PXRD pattern (green) as
compared to the as-synthesized Co-AIM (black) and NU-1000 (blue). c, N2 isotherm (green)
as compared to NU-1000 (red) and the as-synthesized Co-AIM (blue). d, XPS spectrum of
Co-AIM+NU-1000 in the Co 2p region. The highlighted feature is indicative of the presence
of Co(III). ............................................................................................................................... S14
Figure S19. Characterization of Co-SIM+NU-1000 after catalysis: a, SEM-EDS line scan of
Co (blue) and Zr (green) and a baseline (red) b. PXRD pattern (purple) as compared to that of
NU-1000 (blue) and Co-SIM+NU-1000 before catalysis (green). c, N2 isotherm (blue) as
compared to that of the parent MOF (green) and Co-SIM+NU-1000 (red) before catalysis. d,
XPS spectrum of Co-SIM+NU-1000 in the Co 2p region. The feature highlighted in the box
indicates the appearance of Co(III). ....................................................................................... S15
Figure S20. Dehydrated cluster model of Co deposited on NU-1000. .................................. S16
Figure S21. (a) Structures for A-1-(S=5/2) and A-1-(S=3/2) and (b) proposed electronic
configurations based on Mulliken spin densities. .................................................................. S17
List of Tables
Table S1. EXAFS fitting parameters for Co(OH)2. ................................................................. S9
Table S2. Fitting results for the as-synthesized and activated Co-SIM+NU-1000, Co-
AIM+NU-1000 and Co-ZrO2. ................................................................................................ S13
Table S3. Electronic energies in kcal mol–1 at different levels of theory. ............................. S17
Table S4. Charge analysis and spin densities at the M06-L/BS1 level of theory. <S2>
represents the spin operator expectation value. SUM(HSD) stands for sum overall Hirshfeld
spin densities and SUM(MSD) stands for sum overall Mulliken spin densities. Atom labeling
is presented in Figure S21. ..................................................................................................... S18
Table S5. Electronic energies and enthalpies at M06-L/BS1. <S2> represents the spin operator
expectation value. ................................................................................................................... S20
Table S6. Electronic energies at the M06-L/BS2, B3LYP-D3/BS1, and TPSSh/BS1. <S2>
represents the spin operator expectation value. ...................................................................... S20
S4
Materials
Zirconyl chloride octahydrate, 1,3,6,8-tetrabromopyrene, (4-
(methoxycarbonyl)phenyl)boronic acid, K3PO4, tetrakis(triphenylphosphine) palladium(0),
benzoic acid, hydrochloric acid, hydrogen peroxide, cobalt(II) acetate tetrahydrate, high
purity silica, cobalt and zirconium ICP standards were purchased from Sigma Aldrich
Chemicals Company, Inc. (Milwaukee, WI) and were used as received. Ligand for NU-1000,
1,3,6,8-tetrakis(p-benzoic acid)pyrene, was synthesized by a published procedure and its
purity confirmed by 1H-NMR spectroscopy. Concentrated sulfuric acid was purchased from
VWR Scientific, LLC (Chicago, IL). Compound bis(N,N’-di-isopropyl-acetamidinato)Co(II)
(98%) was obtained from Strem Chemicals, and used without further purification. Acetone,
chloroform, 1,4-dioxane, N,N-dimethylformamide (DMF), tetrahydrofuran (THF) were
obtained from Fisher Scientific and used without further purification. Ultrapure deionized
water (18.2 MB•cm resistivity) was obtained from a Millipore Milli-Q Biocel A10 instrument
(Millipore Inc., Billerica, MA).
All gases used for the adsorption and desorption measurements were Ultra High Purity Grade
5 and were obtained from Airgas Specialty Gases (Chicago, IL).
Physical methods and measurements
Atomic layer deposition of cobalt in NU-1000 was carried out on a Savannah 100 (Cambridge
Nanotech, Inc).
Powder X-ray diffraction (PXRD) patterns were recorded on a Rigaku X-ray Diffractometer
Model ATX-G (Tokyo, Japan) equipped with an 18 kW Cu rotating anode, an MLO
monochromator, and a high-count-rate scintillation detector. Measurements were made over
the range 2°<2θ< 15° in 0.05° step width with a 3°/min scanning speed.
N2 adsorption and desorption isotherms were measured on a Micromeritics Tristar II 3020
(Micromeritics, Norcross, GA) instrument at 77 K. Pore-size distributions were obtained
using DFT calculations using a carbon slit-pore model with a N2 kernel. Before each run,
samples were activated at 120 °C for 12–24 h under high vacuum on a Smart Vacprep from
Micromeritics. Around 50 mg of sample was used in each measurement and BET surface area
was calculated in the region P/P0 = 0.005–0.05.
Inductively coupled plasma atomic–emission spectroscopy (ICP–AES) was conducted on an
iCAP™ 7600 ICP-AES Analyzer (Thermo Scientific™) over the 166–847nm spectral range.
Samples (2–3 mg) were digested in a small amount (1 mL) of a mixture of 3:1 v/v conc.
H2SO4:H2O2 (30 wt % in H2O) by heating in a Biotage (Uppsala, Sweden) SPX microwave
reactor (software version 2.3, build 6250) at 150 °C for 5 minutes. The acidic solution was
then diluted to a final volume of 15 mL with Millpore H2O and analyzed for Co (228.616,
237.862 and 238.892nm) and Zr (327.305, 339.198, and 343.823 nm) content as compared to
standard solutions.
Scanning electron microscopy (SEM) images were collected on a Hitachi SU8030 FE-SEM
(Dallas, TX) microscope at Northwestern University’s EPIC/NUANCE facility. Samples
S5
were coated with OsO4 to ~20 nm thickness in a Denton Desk III TSC Sputter Coater
(Moorestown, NJ) before imaging.
Diffuse reflectance infrared spectra (DRIFTS) were recorded on a Nicolet 6700 FTIR
spectrometer (Thermo Scientific) equipped with an MCT detector and a Harrick praying
mantis accessory. Samples were activated at 120 °C under high vacuum for 24 h before each
measurement. The spectra were collected at 1 cm−1 resolution over 64 scans. A sample of
solid KBr was utilized as the background.
Thermogravimetric analysis (TGA) was performed on a TA Instruments Q500 in a flow of N2
at a heating rate of 10 °C/min from 25 to 600 °C.
Temperature Programmed Oxidation (TPO) profile diagram of the samples was collected on
AutoChem 2920. Before the TPO process, the sample was heated in He flow for 2 hours at
120 °C to remove any physisorbed water. Under a flow of 10% O2/He, the sample was heated
to 300 °C at a heating rate of 2 °C/min. The signal was recorded with a thermal conductivity
detector (TCD).
X-ray photoelectron spectroscopy (XPS) measurements were carried out at the KECK-
II/NUANCE facility at NU on a Thermo Scientific ESCALAB 250 Xi (Al Kα radiation, hν =
S5 1486.6 eV) equipped with an electron flood gun. XPS data was analyzed using Thermo
Scientific Avantage Data System software and all spectra were referenced to the C1s peak
(284.8 eV).
Catalyst activity and selectivity measurements were recorded using a packed-bed flow reactor
(Microactivity Efficient, MAE). Using an Agilent 7890A GC system, the amount of propane
and propene were analyzed by an FID detector using an Agilent J&W GC column (GS-
Alumina, 30 m X 0.535 mm); the amount of CO2 and CO is determined by a TCD detector
using a combination of two columns (Column 1: HP-Plot Q, Column 2: HP-Plot Molesieve).
The amounts of the gases were determined based on the integration areas converted to mol%
using relevant calibration curves.
Ambient temperature x-ray powder diffraction measurements were performed at beamline 17-
BM-B at the Advanced Photon Source at Argonne National Laboratory. Diffraction patterns
were collected on an amorphous silicon area detector at a nominal sample-detector distance of
1 m. Sample-detector distance, beam center, detector tilt and rotation, and angular corrections
were determined via calibration with NAC (Na2Ca3Al2F14) in GSAS-II.
1 Diffraction images were processed in QXRD and subsequently reduced to one-dimensional
patterns in GSAS-II.2 Lattice parameters and Bragg scattering intensities of reflections out to
2θ=10° were extracted via Le Bail whole pattern fitting of the previously reported NU-1000
crystal structure to diffraction data.345 Structure envelopes (SEs) encompassing regions of
high electron density were generated from extracted peak intensities as previously
described.67 Reflections out to {6 -1 0} (lmax=2) were utilized to improve resolution along the
c axis. To isolate contributions from species added during deposition, difference envelope
densities (DEDs) were calculated via subtraction of the SE of the parent material from those
of metalated MOFs.7
S2
X-ray absorption spectroscopy (XAS) measurements at the Co K-edge (7709 eV) were
performed on the insertion device beamline of the Materials Research Collaborative Access
Team (MRCAT, Sector 10-ID) at the Advanced Photon Source (APS), Argonne National
Laboratory. The beamline was detuned to 50% in order to minimize the presence of
harmonics. Data was acquired in transmission in step-scan mode in about 10 min using
ionization chambers optimized for the maximum current with linear response (~1010 photons
detected/sec) with 10% absorption in the incident ion chamber and 70% absorption in the
transmission X-ray detector. A Co foil spectrum was acquired simultaneously with each
sample measurement for energy calibration. Samples were pressed into a cylindrical sample
holder consisting of six wells, forming a self-supporting wafer with a thickness chosen to give
an edge step of ~1.0.
The samples were activated in a flow of 3% propane/He and 10% O2/He at 230 °C for 4 hours
and then put on the beamline for measurements in the same gas mixture.
Gas-phase catalysis
The gases used for gas-phase oxidative dehydrogenation of propane catalysis were 3%
propane balanced with Ar and 10% O2 balanced with He.
The catalyst (~80–100 mg Co-AIM+ or Co-SIM+NU-1000, diluted with ~600 mg of high
purity, low surface area SiO2) was packed on quartz wool in a stainless reactor. The reaction
temperature was controlled with a K-type thermocouple at the top of the catalyst bed. For the
catalyst pretreatment procedure, the temperature was ramped at 10 °C/min to 180 °C and then
2 °C/min to a final temperature of 230 °C under a flow of 48 mL/min O2 (10% diluted with
He) and 96 mL/min of C3H8 (3%, diluted with Ar) (2 bar pressure) until the propane
conversion is constant (usually takes 4 hours for Co-AIM+NU-1000 and 6 hours for Co-
SIM+NU-1000). For the catalysis, the ratio of flow rates between the two reacting gases is
kept constant for all the experiments, in which the mol ratio of C3H8:O2 is 6:5. Further tests,
in which the amount of catalyst and the flow of the gases were increased to 1.5 of their
original values, were carried out to ensure that the kinetic data were recorded in a reaction-
rate-limited regime, viz, no mass transfer limitation. The rates used in the Arrhenius plot were
recorded in the differential conversion regime (< 10% conversion). Control experiments
where the feed gases were Ar and O2 and the used materials in the catalytic reactor were NU-
1000, Co-SIM+NU-1000 and Co-AIM+NU-1000 were also conducted.
For NU-1000, we only observed CO2 formation in the first 40 minutes’ time on stream (TOS)
from the GC injection. For Co-AIM+ and Co+SIM+NU-1000, we observed CO2 formation
for only the first 3 and 5 hours TOS, respectively.
For both catalysts, a chemical formula of [Zr6(μ3-O)8(OH)8Co4(H2O)8](TBAPy)2 was used as
a close estimation to calculate the molecular weight of the two materials; the TOFs are
determined on a per Cobalt atom basis.
S3
Syntheses
The parent MOF, NU-1000, was synthesized via a literature reported procedure. 8 Upon
thermal activation, the integrity and quality of the obtained material was confirmed by N2
isotherm measurements at 77 K and PXRD. High surface area ZrO2 was synthesized
according to a published procedure and calcined at 600 °C before use.9
Co-SIM+NU-1000: Cobalt(II) acetate tetrahydrate (360.0 mg, 1.45 mmol) was suspended in
40 mL DMF in a 100 mL screw cap jar. It was subsequently incubated in a 100 °C oven for
30 min or until the solution became clear. Next, NU-1000 (400 mg, 0.185 mmol) was added
to the jar and it was subjected to 5 minutes of sonication before being incubated in a 100 °C
oven for 24 h. The suspension was transferred to a centrifuge tube and the mother liquor was
decanted while hot after centrifuge. The solid residue was washed with hot DMF three times
(3 × 50 mL) or until the DMF solution was colorless. The recovered solid material was then
immersed in acetone for an hour and then washed three times (30 min intervals) to exchange
out the residual DMF solvent. After subsequent suspension in acetone for another 8 h, the
green solid material was put in a vacuum oven for 2 h before it was activated at 120 °C on a
smart vacuum prep instrument for 24 h. The recovered material, denoted as Co-SIM+NU-
1000, was kept in a vacuum desiccator for storage. The cobalt amount in the material is
determined to be 4.0 ± 0.3 Co per Zr6 node via ICP-AES.
Co-AIM+NU-1000: Compound bis(N,N′-diiso-propyl-acetamidinato)Co(II), Co(MeC(Ni-
Pr)2)2 (reactant A, Figure S1), was chosen as the Co precursor from our previous work for
CoS-AIM and Co-AIM. 10 , 11 Room temperature deionized H2O is used as a coreactant
(reactant B), instead of the H2S in our previous work, to produce the Co–O(H) motif. In a
typical experiment, a custom-made stainless steel powder sample holder containing
microcrystalline NU-1000 (60.0 mg, 0.028 mmol) was placed in the ALD chamber, which
was held at 125 °C for 30 min to remove any physisorbed water before dosing with the Co
precursor. A cylinder containing Co(MeC(Ni-Pr)2)2 is held at 120 °C, and each of its pulses
followed the time sequence of t1−t2−t3, where t1 is the precursor pulse time, t2 is the substrate
exposure time, and t3 is the N2 purge time (t1 = 1 s, t2 = t3 = 300 s). To ensure full metalation
of the Zr6 sites throughout the microcrystals, the Co(MeC(Ni-Pr)2)2 pulsing cycle was run 60×
before exposing the MOF to H2O pulses, which adopts the same time sequence as the Co
pulse (t1 = 0.015 s, t2 = t3 = 120 s). The typical cobalt content in Co-AIM+NU-1000 is
determined to be 4.0 ± 0.5 per Zr6 node from ICP-AES measurements.
Co-ZrO2: Cobalt(II) acetate tetrahydrate (250.0 mg, 1.0 mmol) was dissolved in 30 mL
Millipore H2O and 600 mg of high surface area ZrO2 was subsequently added to the solution,
forming a suspension. Under constant stirring, it was gradually heated to and maintained at 95
°C to let the water slowly evaporate. Upon the complete evaporation of the solvent, the
remaining solid was collected and calcined in a 600 °C oven for 3 hours (5 °C/min heating
rate) in air.
Characterization
The characterization techniques for both Co-AIM and Co-SIM+NU-1000 are the same,
therefore only the description for Co-AIM+NU-1000 (Figure S2) is detailed in the following
section. The characterization data for Co-SIM+NU-1000, however, is included as Figure S3.
S4
After anchoring Co to NU-1000 via AIM, the crystallinity of Co-AIM is retained, as
can be seen from the PXRD pattern. Upon digestion, the Co content in the samples is
determined by ICP−AES and it is consistently 4.0 ± 0.5 Co atoms for each Zr6 node (9.8 ±
1.1% wt. of Co). The deposition of Co(II) is demonstrated to be conformal within each NU-
1000 micro-crystallite, as confirmed via scanning electron microscopy−energy-dispersive X-
ray spectroscopy (SEM−EDS). The surface area of Co-AIM is abstracted from the
Brunauer−Emmett−Teller (BET) analysis of the N2 isotherm of an activated sample (120 °C,
evacuated for 12 h) and a decrease from 2200 to 1200 m2•g−1 as compared to undecorated
NU-1000 is observed. This is not surprising due to the incorporation of Co (II) and is also in
line with our previous findings (Figure S2).12 Pore-size distributions calculated from DFT
analysis show a decrease in the diameter of the hexagonal pores from 29 to 27 Å (Figure S4).
The valence of the cobalt ions in Co-AIM is determined by X-ray photoelectron spectroscopy
(XPS), from which we can clearly observe a peak at 779.7 eV as well as a satellite peak at ~
785 eV, which can be assigned as Co(II) (Figure S2). In its diffuse reflectance infrared
Fourier transform spectrum (DRIFTS), a decrease in the intensity of the peak at ~3674 cm−1,
along with the disappearance of the hydrogen-bonded −OH/−H2O stretching at 2745, 2747,
and 2551 cm−1, was observed for the Co-AIM material as compared to that of NU-1000,
indicative that the metalation occurs at the −OH2 and −OH sites of the Zr6 node (Figure S5).13
The excellent thermal stability of Co-AIM is shown by the thermal gravimetric analysis, with
little mass loss up to 300 °C under N2 flow (Figure S6).
Figure S1. Structural representation of the used cobalt precursor, bis(N,N′-di-isopropyl-
acetamidinato)Co(II), Co(MeC(Ni-Pr)2)2.
S5
Figure S2. Characterization of Co-AIM+NU-1000 before catalysis: a, SEM-EDS line scan of
Co (red) and Zr (blue) and a baseline (green) b. powder X-ray diffraction pattern (black) as
compared to that of NU-1000 (blue). c, N2 isotherm of Co-AIM (blue) as compared to the
parent MOF, NU-1000 (red). D, XPS scan of the as-synthesized Co-AIM in the Co 2p region.
Figure S3. Characterization of Co-SIM+NU-1000 before catalysis: a, SEM image b. powder
X-ray diffraction pattern (green) as compared to that of NU-1000 (blue). c, N2 isotherm
(green) compared to that of the parent MOF, NU-1000 (blue). d, XPS spectrum of the as-
synthesized Co-SIM+NU-1000 in the Co 2p region.
S6
Figure S4. DFT calculated pore-size distributions of Co-AIM and Co-SIM+NU-1000 before
and after propane ODH catalysis.
Figure S5. DRIFTS spectra of as-synthesized Co-SIM and Co-AIM+NU-1000 as compared
to the parent MOF, NU-1000.
Figure S6. TGA diagram of NU-1000, Co-SIM and Co-AIM+NU-1000 before catalysis
under a flow of N2.
S7
Figure S7. Temperature programmed oxidation data of Co-AIM+NU-1000 and Co-SIM+NU-
1000 as compared to the parent MOF NU-1000.
Figure S8. Oxidative dehydrogenation of propane catalyzed by Co-AIM+NU-1000 (a) and
Co-SIM+NU-1000 (b)at 200 °C where the TOF is determined to be 0.36±0.06 and 0.27±0.09 h−1 for these two materials, respectively.
S8
Figure S9. Characterization of Co-ZrO2 after calcination at 600 °C in air. (a). SEM image (b).
Corresponding elemental map of Co, and (c) elemental map of Zr. (d) N2 isotherms of Co-
ZrO2 at 77 K.
Figure S10. The determination of the TOF for the propane ODH process catalyzed by Co-
ZrO2 at 230 °C.
S9
Figure S11. Delplots for Co-SIM+NU-1000 (a) and Co-AIM+NU-1000 (b) for the oxidative
dehydrogenation of propane.
Data analysis of the XANES and EXAFS region was performed using the
Athena/Artemis/Hephaestus software package14 which makes use of IFEFFIT.15 The XANES
data was processed using standard protocols. The edge energies for all of the samples and
references were calibrated to Co foil. The edge energy was identified as the zero value of the
second derivative of the XANES curve.
Backscattering amplitude and phase shift functions for EXAFS fitting were calculated using
the built-in FEFF function of Artemis. The amplitude reduction factor (S02) used to calculate
the coordination number of Co-O in the chi-difference spectra in Table S1 was calculated
from an Co(OH)2 with a fixed coordination number of 6.
Table S1. EXAFS fitting parameters for Co(OH)2.
Path
Coordination
number (N)
Bond
Distance (R, Å)
Debye-Waller
factor (σ², Å2)
Amplitude
Reduction
Factor (S02)
Edge
Shift (E,
eV)
Co-O 6 2.09 0.008±0.001 0.9682 −5.30±0.82
Co-Co 6 3.17 0.0076±0.0008 0.9682 −5.30±0.82
S10
Figure S12. XANES spectra for Co-SIM, Co-AIM+NU-1000 before and after activation,
along with the data for cobalt reference samples.
Figure S13. Experimental (blue) and fit (orange) data for the Co-ZrO2 before activation in O2
at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d, imaginary part of
R-space.
S11
Figure S14. Experimental (blue) and fit (orange) data for the Co-AIM+NU-1000 before
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space.
Figure S15. Experimental (blue) and fit (orange) data for the Co-SIM+NU-1000 before
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space.
S12
Figure S16. Experimental (blue) and fit (orange) data for the Co-AIM+NU-1000 after
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space.
Figure S17. Experimental (blue) and fit (orange) data for the Co-SIM+NU-1000 after
activation in O2 at 230 °C a, k-space b, magnitude of R-space c, real part of R-space and d,
imaginary part of R-space.
S13
Table S2. Fitting results for the as-synthesized and activated Co-SIM+NU-1000, Co-
AIM+NU-1000 and Co-ZrO2.
Co-AIM Activated
Co-AIM
Co-SIM Activated
Co-SIM
Co-ZrO2
Co–O
coordination
number
4.4±0.3 3.7±0.1 4.4±0.4 3.6±0.3 4.7±0.3
Co–O bond
distance (Å)
2.01 1.95 2.00 1.96 2.00
Debye-
Waller
Factor (σ²,
Å2)
0.0094±0.0010 0.0075±0.0004 0.0088±0.0010 0.0064±0.0010 0.011±0.001
Co–Co
coordination
number
NA 0.55±0.01 NA NA 2.05±1.07
Co–Co
distance (Å)
NA 2.88 NA NA 3.37
Debye-
Waller
Factor (σ²,
Å2)
0.0053±0.0015 0.016±0.006
Co–Zr
coordination
number
NA 1.54±0.27 NA NA NA
Co–Zr
distance (Å)
NA 3.23 NA NA NA
Debye-
Waller
Factor (σ²,
Å2)
0.0136±0.002
S14
Post-Catalysis
The crystallinity, the uniform distribution of the cobalt atoms in Co-AIM and Co-SIM remain
the same as evidenced by the data displayed in Figures S18 and 19. Although there is a slight
decrease in the surface area of Co-AIM after catalysis, we cannot exclude the contamination
from the used quartz wool during the catalysis in the measured sample. From the XPS
spectrum of the Co-AIM, there is appearance of satellite peaks at ~790 and ~805 eV that can
be attributed to the Co(III) species.
Figure S18. Characterization of Co-AIM+NU-1000 after propane ODH catalysis: a, SEM-
EDS line scan of Co (green) and Zr (blue) and a baseline (red) b. PXRD pattern (green) as
compared to the as-synthesized Co-AIM (black) and NU-1000 (blue). c, N2 isotherm (green)
as compared to NU-1000 (red) and the as-synthesized Co-AIM (blue). d, XPS spectrum of
Co-AIM+NU-1000 in the Co 2p region. The highlighted feature is indicative of the presence
of Co(III).
S15
Figure S19. Characterization of Co-SIM+NU-1000 after catalysis: a, SEM-EDS line scan of
Co (blue) and Zr (green) and a baseline (red) b. PXRD pattern (purple) as compared to that of
NU-1000 (blue) and Co-SIM+NU-1000 before catalysis (green). c, N2 isotherm (blue) as
compared to that of the parent MOF (green) and Co-SIM+NU-1000 (red) before catalysis. d,
XPS spectrum of Co-SIM+NU-1000 in the Co 2p region. The feature highlighted in the box
indicates the appearance of Co(III).
Computational modeling
Computational Details
Methodology. All calculations were carried out at the DFT level using the M06-L16 local
density functional as implemented in Gaussian 09. 17 This functional has shown a good
performance in modeling dispersion interactions,16 ,18-19 transition metals,16,18-19 spin states in
cobalt complexes,16,20 zeolites,21 and transition metals supported on NU-1000.12,22 The def2-
SVP basis set was used on H, C, and O atoms, and the def2-TZVPP basis set on Co and Zr
atoms.23,24 The SDD pseudopotential was used to represent the core electrons on Zr atoms.25
This set of basis functions will be referred as BS1. Numerical integrations were performed
with an ultrafine grid. An automatic density-fitting set generated by the Gaussian program
was employed to reduce the computational cost. All geometry optimizations were performed
in the gas phase. The nature of all stationary points and transition states was confirmed by
analytic computation of vibrational frequencies, which were also used to compute
thermochemical quantities at 503.15 K. All frequencies below 50 cm–1 were replaced by 50
cm–1 when computing vibrational partition functions. To test the influence of the basis set,
single-point calculations were performed with def2-TZVP for H, C, and O atoms (same def2-
TZVPP for Co, and def2-TZVPP/SDD for Zr). This set of basis functions will be referred as
BS2. To test the influence of the density functional, single-point calculations with B3LYP-
D3/BS126 -27 and TPSSh/BS128 were performed on all intermediates and transitions states
previously optimized at the M06-L/BS1 level of theory. The B3LYP density functional was
employed by Sauer et al. for studies on oxidative dehydrogenation of propane using vanadium
complexes, whereas the TPSSh density functional has been recommended for iron and cobalt
S16
complexes.29-31 Mulliken charges and spin densities, Hirshfeld charges and spin densities, and
CM5 charges for all species are collected in Table S4.32-33
Cluster Models. For NU-1000, a neutral cluster model formed by one node and eight organic
linkers was extracted from previously reported periodic DFT calculations.13 The mix-S proton
topology was used to describe the node, i.e., [Zr6(μ3−O)4(μ3−OH)4(OH)4(OH2)4]8+.13 The eight
TBAPy4– (1,3,6,8-tetrakis(p-benzoate)pyrene) linkers were truncated to acetate groups.
During the geometry optimization and frequency analysis, methyl groups of the acetate
linkers were kept fixed to account for the rigidity of the solid structure. Due to the high
temperature of the experiments (230 °C, 503.15 K), we assumed a dehydrated pattern for the
cluster models, where the node has lost six water molecules (see arrows in Figure S20).
Figure S20. Dehydrated cluster model of Co deposited on NU-1000.
Oxidation state of cobalt in activated Co-SIM
Figure S21a shows the optimized geometries for A-1-(S=5/2) and A-1-(S=3/2). Interestingly,
one oxygen atom in A-1-(S=3/2) changes its coordination mode from μ3 to μ2 (see
dislocation).34 After the first C–H bond abstraction via A-TS2-3, the node recovers its initial
symmetric configuration.
Figure S21b shows several proposed electronic configurations for A-1 assuming oxidation
states from Co(IV) to Co(II). In A-1-(S=5/2), the spin density on Co is 2.89e and ca. 2
unpaired electrons are delocalized over three oxygen atoms. This scenario is consistent with a
Co(II) high spin compound. In A-1-(S=3/2), the spin density on Co is 2.04e and ca. 1
unpaired electron is delocalized over three oxygen atoms. This scenario is consistent with a
Co(III) intermediate spin species. Regarding enthalpies, Co(III) A-1-(S=3/2) is 8.7 kcal mol–1
more stable than the Co(II) A-1-S(3/2), which is in line with the experimental detection of
Co(III) upon activation.
S17
Co1 O1O2
O3
dislocation
Co1 O1O2
O3
A-1-(S=5/2)
A-1-(S=3/2)
(a) (b)
Figure S21. (a) Structures for A-1-(S=5/2) and A-1-(S=3/2) and (b) proposed electronic
configurations based on Mulliken spin densities.
Influence of basis set and density functionals for Co-SIM
Table S3 collects single-point energies for all species using different levels of theory.
Regarding the basis set, M06-L/BS2 performs similar to M06-L/BS1. Regarding density
functionals at BS1 level, similar trends are found for the functionals considered herein. The
quartet spin state A-1-(S=3/2) is always favored over A-1-(S=5/2). The rate-determining
barrier from A-4 to A-TS4-5 (20.0 kcal mol–1 for M06-L, 17.6 kcal mol–1 for B3LYP-D3,
16.7 kcal mol–1 for TPSSh) and the relative energies between competing transition states A-
TS4-5 and A-TS4-6 (4.5 kcal mol–1 for M06-L, 5.0 kcal mol–1 for B3LYP-D3, 3.1 kcal mol–1
for TPSSh) are similar between functionals.
Table S3. Electronic energies in kcal mol–1 at different levels of theory.
Species M06-L/BS1 M06-L/BS2 B3LYP-D3/BS1 TPSSh/BS1
A-1-(S=5/2) 0.0 0.0 0.0 0.0
A-1-(S=3/2) -9.0 -10.4 -19.9 -18.1
A-2-(S=3/2) -17.1 -18.1 -29.6 -15.7
A-2-(S=5/2) -6.8 -7.2 -10.8 2.4
A-TS2-3-(S=3/2) 0.2 1.9 -15.3 -0.6
A-TS2-3-(S=5/2) 2.4 4.0 -12.0 3.2
A-3-(S=3/2) -15.4 -13.4 -30.0 -12.2
A-4-(S=3/2) -40.2 -37.3 -54.8 -39.9
A-TS4-5-(S=3/2) -20.2 (20.0)a -16.2 (21.1)a -37.2 (17.6)a -23.2 (16.7)a
A-5-(S=3/2) -46.1 -46.9 -73.8 -59.3
A-TS4-6-(S=3/2) -15.7 (4.5)b -12.2 (4.0)b -32.2 (5.0)b -20.0 (3.1)b
A-6-(S=3/2) -70.7 -66.2 -99.4 -75.1 a Relative energy between A-TS4-5 and A-4. b Relative energy between A-TS4-6 and A-TS4-5.
S18
Charges and spin densities
Table S4. Charge analysis and spin densities at the M06-L/BS1 level of theory. <S2> represents the spin operator expectation value. SUM(HSD)
stands for sum overall Hirshfeld spin densities and SUM(MSD) stands for sum overall Mulliken spin densities. Atom labeling is presented in
Figure S21.
Atom
Charges A-1 A-1 A-2 A-2 A-TS2-3 A-TS2-3 A-3 A-4 A-TS4-5 A-5 A-TS4-6 A-6
S 3/2 5/2 3/2 5/2 3/2 3/2 3/2 3/2 3/2 3/2 3/2 3/2
<S2> 3.75 8.75 3.75 8.75 3.77 8.75 3.78 3.75 3.75 3.75 3.75 3.75
Co1
CM5 0.71 0.77 0.67 0.76 0.68 0.68 0.65 0.62 0.57 0.63 0.56 0.62
Hirshfeld 0.38 0.48 0.35 0.47 0.41 0.42 0.4 0.33 0.32 0.43 0.3 0.41
Hirshfeld spin density 2.08 3.02 2.07 3.02 2.74 2.85 2.78 2.38 2.51 2.65 2.45 2.62
Mulliken 0.7 0.78 0.63 0.75 0.72 0.71 0.64 0.65 0.6 0.71 0.58 0.68
Mulliken spin density 2.04 2.89 2.03 2.87 2.73 2.77 2.77 2.39 2.55 2.72 2.5 2.67
O(1)
CM5 -0.5 -0.48 -0.5 -0.48 -0.49 -0.47 -0.49 -0.47 -0.53 -0.61 -0.46 -0.41
Hirshfeld -0.29 -0.29 -0.29 -0.28 -0.29 -0.27 -0.29 -0.26 -0.28 -0.3 -0.27 -0.21
Hirshfeld spin density 0.33 0.68 0.37 0.68 0.64 0.7 0.65 0.52 0.31 0.07 0.24 0.14
Mulliken -0.47 -0.47 -0.47 -0.46 -0.47 0.24 -0.47 -0.46 -0.57 -0.49 -0.51 -0.66
Mulliken spin density 0.36 0.76 0.38 0.77 0.72 0.79 0.74 0.59 0.35 0.07 0.27 0.15
O(2)
CM5 -0.49 -0.49 -0.5 -0.48 -0.47 -0.43 -0.43 -0.59 -0.61 -0.61 -0.6 -0.6
Hirshfeld -0.3 -0.29 -0.38 -0.28 -0.24 -0.23 -0.23 -0.28 -0.3 -0.3 -0.28 -0.28
Hirshfeld spin density 0.37 0.67 0.37 0.66 -0.16 0.72 0.72 0.1 0.09 0.07 0.13 0.11
Mulliken -0.48 -0.47 -0.48 -0.47 -0.55 -0.49 -0.49 -0.48 -0.48 -0.49 -0.49 -0.49
Mulliken spin density 0.41 0.75 0.41 0.75 -0.22 0.81 0.13 0.09 0.09 0.07 0.13 0.11
S19
O(3)
CM5 -0.51 -0.54 -0.51 -0.54 -0.62 -0.63 -0.63 -0.64 -0.64 -0.64 -0.68 -0.67
Hirshfeld -0.24 -0.26 -0.29 -0.26 -0.31 -0.32 -0.33 -0.33 -0.33 -0.33 -0.35 -0.35
Hirshfeld spin density 0.13 0.46 0.35 0.46 0.18 0.22 0.19 0.17 0.17 0.15 0.1 0.07
Mulliken -0.59 -0.65 -0.59 -0.65 -0.72 -0.74 -0.71 -0.67 -0.73 -0.75 -0.74 -0.75
Mulliken spin density 0.14 0.53 0.13 0.53 0.19 0.24 0.21 0.2 0.19 0.16 0.1 0.07
ΣO atoms SUM(HSD) 0.84 1.8 1.1 1.8 0.65 1.63 1.56 0.79 0.57 0.29 0.46 0.31
SUM(MSD) 0.91 2.04 0.93 2.05 0.69 1.84 1.08 0.88 0.62 0.29 0.5 0.33
S20
Energies in Hartrees for all species
Table S5. Electronic energies and enthalpies at M06-L/BS1. <S2> represents the spin operator
expectation value.
Species S <S2> E H (503.15 K) Imaginary
frequency
A-1 3/2 3.75 -4245.130405 -4244.871293 N/A
A-1 5/2 8.75 -4245.116027 -4244.857413 N/A
A-2 3/2 3.80 -4364.177219 -4363.799471 N/A
A-2 5/2 8.75 -4364.160772 -4363.783513 N/A
A-TS2-3 3/2 3.77 -4364.149570 -4363.779276 959.6i
A-TS2-3 5/2 8.75 -4364.146101 -4363.774166 119.1i
A-3 3/2 3.78 -4364.174564 -4363.799401 N/A
A-4 3/2 3.75 -4364.214010 -4363.836932 N/A
A-TS4-5 3/2 3.75 -4364.182195 -4363.811693 1711.7i
A-5 3/2 3.75 -4246.429416 -4246.145168 N/A
A-TS4-6 3/2 3.75 -4364.175043 -4363.800080 360.7i
A-6 3/2 3.75 -4364.262672 -4363.883858 N/A
Propane 0 N/A -119.033918 -118.918090 N/A
Propene 0 N/A -117.799298 -117.708708 N/A
Table S6. Electronic energies at the M06-L/BS2, B3LYP-D3/BS1, and TPSSh/BS1. <S2>
represents the spin operator expectation value.
Species <S2> BS2 <S2> B3LYP-D3 <S2> TPSSh
A-1 3.75 -4247.939954 3.75 -4245.491552 3.75 -4245.325718
A-1 8.75 -4247.923396 8.75 -4245.459904 8.75 -4245.296877
A-2 3.75 -4367.116708 3.75 -4364.568419 3.75 -4364.391397
A-2 8.75 -4367.099308 8.75 -4364.538383 8.75 -4364.362574
A-TS2-3 3.77 -4367.084813 3.78 -4364.545652 3.77 -4364.367432
A-TS2-3 8.75 -4367.081482 8.75 -4364.540381 8.75 -4364.361258
A-3 3.78 -4367.109304 3.78 -4364.568970 3.77 -4364.385837
A-4 3.75 -4367.147345 3.75 -4364.608617 3.75 -4364.430013
A-TS4-5 3.75 -4367.113718 3.75 -4364.580539 3.75 -4364.403301
A-5 3.75 -4249.233521 3.75 -4246.813318 3.75 -4246.627263
A-TS4-6 3.75 -4364.175043 3.75 -4364.572541 3.75 -4364.398341
A-6 3.75 -4367.193406 3.75 -4364.679606 3.75 -4364.486103
Propene N/A -117.929169 N/A -117.825582 N/A -117.833573
Propane N/A -119.164499 N/A -119.061325 N/A -119.069522
S21
XYZ coordinates (Å) for all species
A-1-(S=3/2) SCF=-4245.130405 au
C -4.304430 2.549920 3.199910
C 4.196270 -3.415330 3.024640 C -4.486640 -3.235910 2.911830
C 4.347290 2.140480 3.359610
C 4.209400 -3.082060 -3.181270 C -4.260360 2.880470 -2.833850
C 4.422600 2.478090 -2.850360
C -4.460500 -2.928950 -3.119860 H -4.614760 1.811670 3.952420
H -3.957120 3.444110 3.728290
H -5.187510 2.777240 2.592530 H -5.455470 -3.127980 2.413120
H -4.268350 -4.290730 3.112930
H -4.551350 -2.728310 3.884530 H 3.809500 -4.205790 3.675700
H 4.912270 -3.836360 2.307780
H 4.756010 -2.689280 3.629010 H 4.025310 2.339000 4.387750
H 5.240070 1.506800 3.342220
H 4.606190 3.103250 2.896590 H -5.248600 2.815050 -2.366910
H -3.978410 3.927120 -2.996640
H -4.321140 2.406450 -3.823590 H -4.648970 -2.216610 -3.935410
H -4.183080 -3.886600 -3.573130
H -5.391250 -3.023270 -2.550030
H 4.454930 2.123880 -3.889860
H 4.222710 3.557020 -2.884280
H 5.391460 2.283930 -2.379890 H 3.836140 -3.436910 -4.147380
H 5.051880 -2.394900 -3.321440
H 4.597200 -3.946420 -2.624360 C -3.347430 -2.590580 2.114360
C -3.206660 1.933080 2.390910
C -3.166230 2.111630 -2.125800 C 3.282900 1.756890 -2.163240
C 3.103810 -2.401580 -2.402900
C 3.062620 -2.714220 2.294280 C -3.292630 -2.323740 -2.323360
C 3.193630 1.562970 2.542500 O -1.069860 1.211840 -0.061960
O -3.517360 1.217010 -1.301280
O -3.605870 -1.440350 -1.473120 O -3.592280 1.192930 1.438600
O -2.002020 2.149900 2.681520
O 2.001300 1.823430 2.861720 O 1.847960 -2.887340 2.595060
O 3.539650 0.881490 1.526290
O 3.468160 -1.934570 1.379610 O 3.585620 0.994970 -1.205080
O 3.487610 -1.748280 -1.398420
O 1.890570 -2.494170 -2.778960 O 2.106970 1.951120 -2.600830
O 1.113620 -0.166960 -1.211640
O 1.318170 2.029680 0.118570 O 0.040620 3.585850 1.695070
O 0.222010 3.743790 -1.523350
O 1.136440 -0.344240 1.574330 O -1.298100 -0.324910 1.990270
O -2.147280 -2.978640 2.245310
O -3.702120 -1.644180 1.349060 O -0.722190 -0.113300 -2.768950
O -1.971780 2.354250 -2.443280
O -2.098190 -2.666600 -2.591870 O 1.048910 -2.431510 -0.085170
O -1.276100 -1.653220 -0.210840
Zr 2.588180 -0.466370 0.110360 Zr -0.079780 1.356910 1.763340
S22
Zr 0.036610 1.509910 -1.818240 Zr -0.045920 -1.753510 -1.849940
Zr -2.655790 -0.192060 0.118830
Zr -0.094650 -1.974640 1.479290 Co 0.620720 3.618050 0.110920
A-1-(S=5/2) SCF=-4245.116027 au
C -4.165850 2.905200 3.013270
C 4.083550 -3.405110 3.089030 C -4.585750 -2.875490 3.046880
C 4.463500 2.149780 3.115190
C 4.038640 -3.413460 -3.125650 C -4.177920 2.902590 -3.029730
C 4.480930 2.143150 -3.104420
C -4.616760 -2.900950 -2.992510 H -4.497170 2.222650 3.808230
H -3.776510 3.811920 3.488220
H -5.045900 3.134980 2.402450 H -5.555080 -2.755230 2.551980
H -4.408110 -3.925660 3.303960
H -4.618630 -2.312970 3.990630 H 3.672490 -4.142130 3.786310
H 4.773520 -3.893930 2.389910
H 4.679130 -2.670700 3.647130 H 4.161640 2.417350 4.133730
H 5.329560 1.479940 3.124480
H 4.755790 3.074270 2.597330 H -5.162520 2.903330 -2.550720
H -3.855690 3.926100 -3.252640
H -4.269210 2.377770 -3.991160 H -4.785430 -2.227150 -3.844410
H -4.383560 -3.892500 -3.394690
H -5.543850 -2.925390 -2.409770
H 4.486830 1.731410 -4.123000
H 4.324520 3.225850 -3.196020
H 5.446410 1.935350 -2.632930 H 3.640190 -3.805040 -4.067200
H 4.906590 -2.770120 -3.311430
H 4.397520 -4.261090 -2.525500 C -3.410080 -2.305100 2.240850
C -3.084640 2.168240 2.255570
C -3.108290 2.156200 -2.258640 C 3.305810 1.549670 -2.341570
C 2.948450 -2.672970 -2.357390
C 2.971110 -2.684510 2.332310 C -3.425740 -2.326040 -2.210390
C 3.287150 1.545550 2.363670
O -1.002380 1.347040 -0.003170 O -3.491120 1.361750 -1.354760
O -3.706380 -1.406450 -1.389480
O -3.468560 1.375180 1.350310 O -1.877860 2.352780 2.585410
O 2.110270 1.859400 2.720310 O 1.752190 -2.806260 2.669280
O 3.583380 0.802860 1.386060
O 3.381870 -1.959580 1.382300 O 3.593820 0.797240 -1.368450
O 3.369740 -1.959140 -1.405600
O 1.723600 -2.796960 -2.677870 O 2.132090 1.857680 -2.711620
O 1.126830 -0.311530 -1.538510
O 1.451670 1.798780 -0.001890 O 0.275070 3.647360 1.514400
O 0.270580 3.637040 -1.533450
O 1.133660 -0.311580 1.539710 O -1.235010 -0.187650 2.085700
O -2.231670 -2.733750 2.465200
O -3.696830 -1.392190 1.415850 O -1.244520 -0.194660 -2.084650
O -1.899820 2.344790 -2.583530
O -2.248480 -2.749760 -2.445480 O 0.967710 -2.365620 0.000840
O -1.401680 -1.789590 0.004680
Zr 2.480750 -0.543260 -0.000870 Zr 0.023890 1.447200 1.771300
S23
Zr 0.016680 1.443450 -1.776580 Zr -0.190600 -1.885150 -1.654280
Zr -2.575400 -0.095350 0.001140
Zr -0.183420 -1.881920 1.658050 Co 1.091890 3.577180 -0.009880
A-2-(S=3/2) SCF=-4364.177219 au
C 4.794540 0.354290 -3.205570
C -5.414820 -1.545960 -3.015290 C 2.559980 -4.985660 -2.912080
C -3.247380 3.571670 -3.355060
C -5.279790 -1.235080 3.190380 C 4.900160 0.676050 2.827900
C -3.167160 3.912530 2.854390
C 2.672140 -4.693130 3.119260 H 4.769580 -0.446460 -3.957630
H 4.848810 1.311790 -3.734380
H 5.693180 0.195030 -2.599280 H 3.487010 -5.289050 -2.414570
H 1.923560 -5.854710 -3.112040
H 2.828230 -4.550820 -3.885400 H -5.391680 -2.425870 -3.666020
H -6.239880 -1.631780 -2.297160
H -5.623660 -0.653360 -3.619570 H -2.873490 3.618100 -4.383920
H -4.322600 3.365510 -3.336140
H -3.082760 4.555130 -2.892880 H 5.771390 0.206060 2.359940
H 5.078110 1.745240 2.990260
H 4.760070 0.219660 3.818120 H 3.140220 -4.122660 3.933970
H 2.023000 -5.449000 3.573680
H 3.479050 -5.165100 2.548530
H -3.342080 3.603970 3.894350
H -2.537540 4.811170 2.887170
H -4.129840 4.137630 2.385250 H -5.086010 -1.712220 4.156430
H -5.760920 -0.259990 3.330820
H -5.992000 -1.860610 2.634780 C 1.791750 -3.924420 -2.115480
C 3.540950 0.246460 -2.394700
C 3.585570 0.429180 2.121260 C -2.428140 2.785210 2.165810
C -3.992690 -1.070960 2.411870
C -4.092160 -1.375790 -2.288520 C 1.858330 -3.657550 2.324360
C -2.434930 2.569750 -2.538090
O 1.309580 0.480930 0.058500 O 3.534620 -0.530090 1.296950
O 2.508100 -2.983790 1.472300
O 3.588910 -0.583480 -1.439820 O 2.534520 0.941570 -2.687710
O -1.244690 2.310000 -2.863770 O -3.058300 -2.035120 -2.591280
O -3.025940 2.098170 -1.515860
O -4.139160 -0.496590 -1.375530 O -3.015110 2.221540 1.202420
O -4.073920 -0.314160 1.410030
O -2.925710 -1.656550 2.785790 O -1.280340 2.472800 2.607880
O -1.253650 0.141500 1.207620
O -0.481000 2.242490 -0.112230 O 1.265610 3.088360 -1.738540
O 1.191100 3.290700 1.544030
O -1.354380 -0.012250 -1.571040 O 0.866450 -1.012520 -1.987370
O 0.539170 -3.779380 -2.246320
O 2.508410 -3.209670 -1.351850 O 0.441710 -0.579450 2.764230
O 2.602430 1.148200 2.440940
O 0.630590 -3.474200 2.596790 O -2.142680 -1.937480 0.086580
O 0.296300 -2.218000 0.212320
Zr -2.727550 0.469080 -0.106020 Zr 0.455080 1.033430 -1.763930
S24
Zr 0.420000 1.222070 1.812770 Zr -0.856610 -1.782420 1.853000
Zr 2.157190 -1.455060 -0.120950
Zr -0.909990 -2.007430 -1.477380 Co 0.852690 3.374100 -0.118560
C 4.210350 2.753390 -0.208330
H 3.258840 2.220390 -0.048350 H 5.003140 2.100580 0.187350
H 4.351510 2.826970 -1.297640
C 4.228630 4.120890 0.446690 H 3.972890 4.026150 1.515420
H 5.257650 4.518830 0.424220
C 3.321950 5.146400 -0.201110 H 2.243020 4.965350 -0.000420
H 3.491560 6.157510 0.194670
H 3.430200 5.177150 -1.294380
A-2-(S=5/2)
SCF=-4364.160772 au C 4.751720 0.404530 -3.196060
C -5.449410 -1.522570 -2.878770
C 2.534440 -4.942610 -2.904100 C -3.299330 3.602390 -3.217540
C -5.231000 -1.247990 3.326210
C 4.938370 0.690770 2.837300 C -3.135720 3.906770 2.992240
C 2.727640 -4.685450 3.126830
H 4.718500 -0.391840 -3.952490 H 4.796500 1.365250 -3.719850
H 5.658900 0.243890 -2.602990
H 3.468840 -5.246690 -2.421010 H 1.897420 -5.812150 -3.100560
H 2.788360 -4.501460 -3.878350
H -5.432990 -2.398590 -3.534970
H -6.264480 -1.614690 -2.150070
H -5.668630 -0.626970 -3.474900
H -2.939530 3.655870 -4.251020 H -4.373670 3.393410 -3.185240
H -3.130860 4.583540 -2.751730
H 5.804330 0.225790 2.354770 H 5.115880 1.759400 3.003320
H 4.812830 0.228310 3.826520
H 3.205340 -4.118720 3.938470 H 2.086550 -5.445700 3.585500
H 3.527870 -5.152110 2.542400
H -3.295740 3.591620 4.032620 H -2.507920 4.806800 3.021810
H -4.105240 4.132190 2.537550
H -5.022990 -1.730410 4.286690 H -5.712570 -0.275020 3.478980
H -5.949180 -1.872050 2.776580
C 1.763660 -3.866330 -2.126500 C 3.477330 0.269640 -2.393660
C 3.625730 0.466580 2.114340 C -2.374580 2.812210 2.259410
C -3.947900 -1.114870 2.512130
C -4.110360 -1.342760 -2.169440 C 1.898170 -3.676100 2.318280
C -2.496660 2.571760 -2.438690
O 1.316140 0.583590 -0.083460 O 3.582880 -0.464320 1.262110
O 2.536820 -3.023390 1.444030
O 3.491430 -0.563580 -1.444020 O 2.470910 0.957560 -2.731340
O -1.315460 2.304790 -2.818290
O -3.085790 -2.014380 -2.505690 O -3.064840 2.090110 -1.418620
O -4.124370 -0.466220 -1.259310
O -2.996770 2.224500 1.329860 O -4.032470 -0.336400 1.522240
O -2.899650 -1.759470 2.834380
O -1.178100 2.575700 2.607990 O -1.286990 0.133230 1.549540
O -0.670160 2.093060 -0.100460
O 1.165840 3.132680 -1.725370 O 1.250450 3.265770 1.325840
S25
O -1.381760 -0.012810 -1.516000 O 0.772080 -0.992860 -2.082910
O 0.512050 -3.729990 -2.320960
O 2.453540 -3.140690 -1.355830 O 0.899990 -0.799890 2.082540
O 2.642250 1.199430 2.427600
O 0.663560 -3.512580 2.582650 O -2.109610 -1.849080 0.131750
O 0.266220 -2.396660 0.085680
Zr -2.646320 0.462090 0.036600 Zr 0.390730 1.045730 -1.856490
Zr 0.498090 1.211820 1.686700
Zr -0.811540 -1.856950 1.751700 Zr 2.073980 -1.412180 -0.011390
Zr -0.913240 -2.012210 -1.554490
Co 0.453690 3.515890 -0.193350 C 4.366250 2.653840 -0.254530
H 3.320100 2.330440 -0.372380
H 4.934830 1.793830 0.130580 H 4.749610 2.869760 -1.265020
C 4.464260 3.867940 0.647850
H 3.970500 3.645740 1.608560 H 5.521720 4.073880 0.891000
C 3.842890 5.108050 0.038830
H 2.785820 4.934610 -0.220380 H 3.876640 5.970490 0.719460
H 4.347130 5.400630 -0.894890
A-3-(S=3/2)
SCF=-4364.174564 au
C 4.804680 0.761790 -3.071760 C -5.282780 -1.712000 -3.023290
C 2.871870 -4.702020 -3.003680
C -3.404440 3.528080 -3.147240
C -5.192260 -1.640680 3.190490
C 4.865970 0.848840 2.970410
C -3.370300 3.626040 3.071640 C 2.941310 -4.643550 3.035180
H 4.827850 -0.008640 -3.854970
H 4.807410 1.741030 -3.562050 H 5.708160 0.628960 -2.466390
H 3.812290 -4.972790 -2.512460
H 2.285990 -5.596750 -3.241850 H 3.119460 -4.214690 -3.957290
H -5.207550 -2.562770 -3.708040
H -6.104870 -1.872190 -2.314590 H -5.538740 -0.809210 -3.593400
H -3.029280 3.636240 -4.170740
H -4.466400 3.261620 -3.143270 H -3.297190 4.500150 -2.645310
H 5.764160 0.447300 2.489900
H 4.982900 1.919030 3.175630 H 4.747370 0.346520 3.940780
H 3.373150 -4.080710 3.874750 H 2.333620 -5.452020 3.455190
H 3.775880 -5.046740 2.451550
H -3.532100 3.267150 4.097320 H -2.792200 4.556460 3.143810
H -4.342040 3.815440 2.605330
H -4.976210 -2.144420 4.138210 H -5.727940 -0.700500 3.366170
H -5.865890 -2.282560 2.605970
C 2.029300 -3.694050 -2.213250 C 3.527020 0.517430 -2.292730
C 3.583670 0.580070 2.202140
C -2.546600 2.593960 2.317500 C -3.904830 -1.422150 2.396270
C -3.966280 -1.487820 -2.276630
C 2.071940 -3.650080 2.250190 C -2.567040 2.518090 -2.378900
O 1.434440 0.732910 -0.024400
O 3.613260 -0.331960 1.338570 O 2.683340 -2.949750 1.397650
O 3.587670 -0.346080 -1.375330
O 2.487110 1.160620 -2.625020 O -1.361340 2.338480 -2.725250
S26
O -2.907180 -2.108440 -2.609060 O -3.139410 1.962880 -1.398760
O -4.037670 -0.638290 -1.345050
O -3.131090 2.000260 1.367030 O -4.006650 -0.608980 1.438120
O -2.840050 -2.048650 2.707320
O -1.346360 2.408240 2.676170 O -1.317540 -0.021930 1.589830
O -0.714360 1.993370 0.001630
O 1.027690 3.287420 -1.681430 O 1.034380 3.316920 1.606350
O -1.327610 -0.048450 -1.562330
O 0.920570 -0.899510 -1.938500 O 0.780620 -3.600030 -2.458320
O 2.659110 -2.978620 -1.387860
O 0.949390 -0.848020 1.945040 O 2.560940 1.276630 2.501050
O 0.829890 -3.547960 2.522380
O -1.992830 -1.952260 0.035650 O 0.388430 -2.504520 0.024080
Zr -2.621470 0.336380 0.011310
Zr 0.387720 1.134200 -1.741640 Zr 0.393820 1.153240 1.690640
Zr -0.731160 -1.994020 1.665580
Zr 2.122510 -1.306340 -0.010400 Zr -0.753870 -2.026470 -1.612120
Co 0.357920 3.572270 -0.142870
C 3.997850 3.098610 -0.188220 H 3.175980 2.371930 -0.009970
H 4.921650 2.594050 0.131550
H 4.015410 3.233460 -1.280600 C 3.771220 4.376000 0.513760
H 1.958490 3.506300 1.827460
H 4.161640 4.500510 1.532410
C 2.924740 5.433380 -0.048760
H 1.825680 5.219550 0.093120
H 3.080050 6.414080 0.419670 H 3.029340 5.519950 -1.140190
A-4-(S=3/2) SCF=-4364.214010 au
C 2.805480 -4.319990 2.798460
C -2.396360 4.655600 3.305650 C 5.405390 0.838540 3.271350
C -4.875030 -0.314490 2.909800
C -2.139830 5.066500 -2.890250 C 3.023790 -3.913300 -3.226830
C -4.676470 0.119130 -3.291400
C 5.649830 1.258840 -2.748540 H 3.345540 -3.872720 3.644650
H 2.082670 -5.037320 3.201410
H 3.550810 -4.828490 2.176980 H 6.271060 0.388750 2.774090
H 5.634710 1.856350 3.606050 H 5.188150 0.244170 4.170020
H -1.758560 5.128980 4.058920
H -2.822390 5.418120 2.641730 H -3.246490 4.170530 3.803410
H -4.733530 -0.745880 3.906840
H -5.418370 0.634450 2.965000 H -5.481190 -1.018280 2.321950
H 3.916120 -4.324840 -2.743800
H 2.342040 -4.716690 -3.528230 H 3.341840 -3.400130 -4.145290
H 5.576550 0.631230 -3.648060
H 5.827890 2.288560 -3.075970 H 6.495130 0.885540 -2.160610
H -4.489420 0.569460 -4.276050
H -4.943430 -0.931590 -3.463810 H -5.504240 0.649640 -2.810970
H -1.589880 5.337620 -3.797280
H -3.181030 4.820420 -3.128890 H -2.167010 5.944280 -2.229710
C 4.127430 0.818640 2.424160
C 2.135600 -3.161690 2.089570 C 2.301760 -2.872660 -2.392480
S27
C -3.392080 0.160730 -2.474100 C -1.442800 3.914310 -2.166230
C -1.619290 3.614500 2.499890
C 4.300090 1.132660 -2.026810 C -3.534570 -0.171450 2.203140
O 0.642200 -1.654860 -0.117240
O 2.955480 -2.326730 -1.469930 O 4.188630 0.140700 -1.256750
O 2.842670 -2.532830 1.254410
O 0.944050 -2.872940 2.406490 O -2.588940 -0.941880 2.537720
O -0.453410 3.248640 2.846360
O -3.494790 0.688200 1.276570 O -2.248860 3.159010 1.502970
O -3.408010 0.892520 -1.443320
O -2.140550 3.349750 -1.279290 O -0.247310 3.592510 -2.461440
O -2.417570 -0.547180 -2.860630
O -0.696980 0.999950 -1.541950 O -1.741330 -1.056000 -0.169810
O -1.521670 -3.264070 1.375460
O -1.460650 -3.019150 -2.005580 O -0.802650 0.775770 1.562500
O 1.357010 -0.280560 1.932960
O 3.182820 1.630960 2.703030 O 4.083750 -0.054990 1.517240
O 1.482620 -0.020450 -1.916060
O 1.096840 -2.601040 -2.705040 O 3.372690 1.974460 -2.270800
O 0.173150 2.708020 0.167120
O 2.223980 1.371410 0.145580 Zr -1.910430 1.591770 0.021750
Zr -0.460710 -1.292250 1.577660
Zr -0.356580 -1.037750 -1.804870
Zr 1.140580 1.947940 -1.492790
Zr 2.563720 -0.715250 0.018390
Zr 1.023660 1.722620 1.768380 Co -2.021440 -3.033620 -0.201510
H -0.858710 -3.710350 -2.312100
C -3.950790 -3.541210 -0.050850 H -3.843580 -4.464890 -0.651210
C -4.403350 -3.795110 1.348520
H -3.886240 -4.645290 1.806540 H -4.239220 -2.922780 1.994000
H -5.486600 -4.015660 1.347750
C -4.588210 -2.420230 -0.808060 H -4.128620 -2.283380 -1.796120
H -5.656630 -2.651450 -0.978270
H -4.536590 -1.463270 -0.267210
A-5-(S=3/2)
SCF=-4246.424081 au C -4.135170 2.971110 2.992020
C 4.042350 -3.431280 3.114740 C -4.620400 -2.803930 3.075600
C 4.485180 2.119010 3.093040
C 3.991510 -3.492130 -3.099560 C -4.153060 2.916970 -3.050660
C 4.496620 2.059090 -3.126170
C -4.657470 -2.880770 -2.963290 H -4.473400 2.299170 3.793180
H -3.735150 3.877420 3.458900
H -5.013190 3.205590 2.380120 H -5.588760 -2.676970 2.580500
H -4.454360 -3.853840 3.341460
H -4.645990 -2.233060 4.014500 H 3.623740 -4.157580 3.818690
H 4.726160 -3.933750 2.419270
H 4.646780 -2.698830 3.666070 H 4.187280 2.398750 4.109520
H 5.343600 1.439540 3.107400
H 4.787420 3.035680 2.567040 H -5.137130 2.932940 -2.570790
H -3.819500 3.934820 -3.282600
H -4.251220 2.385010 -4.007450 H -4.819290 -2.212330 -3.820840
S28
H -4.435850 -3.878230 -3.357230 H -5.584190 -2.889700 -2.379640
H 4.496820 1.638550 -4.141290
H 4.352310 3.142610 -3.227000 H 5.460100 1.844420 -2.653850
H 3.587720 -3.887270 -4.037370
H 4.866480 -2.860330 -3.291590 H 4.341330 -4.338660 -2.492460
C -3.437860 -2.251980 2.269020
C -3.073920 2.215400 2.220240 C -3.098980 2.165130 -2.259080
C 3.325400 1.481520 -2.346970
C 2.906780 -2.742600 -2.327160 C 2.933910 -2.711840 2.345440
C -3.456780 -2.313530 -2.192470
C 3.312410 1.514290 2.339700 O -1.081570 1.478480 -0.026050
O -3.503260 1.362410 -1.380760
O -3.725520 -1.399830 -1.365660 O -3.484940 1.404310 1.350280
O -1.856280 2.423130 2.514760
O 2.139560 1.848220 2.677410 O 1.713360 -2.839630 2.678590
O 3.610870 0.748880 1.378740
O 3.347950 -1.993450 1.393010 O 3.617030 0.712790 -1.387890
O 3.332130 -2.019800 -1.385950
O 1.679190 -2.881470 -2.638400 O 2.153020 1.814490 -2.693490
O 1.123870 -0.383110 -1.577840
O 1.398780 1.714170 -0.015330 O 0.378570 3.666140 1.689370
O 0.344780 3.639330 -1.721080
O 1.131610 -0.349090 1.583270
O -1.271990 -0.161940 1.946840
O -2.260490 -2.673120 2.523930
O -3.717940 -1.363360 1.419760 O -1.278820 -0.212220 -1.963350
O -1.879300 2.375490 -2.556380
O -2.283030 -2.741120 -2.450740 O 0.938680 -2.391250 0.022000
O -1.448400 -1.883680 0.020280
Zr 2.461960 -0.552560 0.004340 Zr 0.055520 1.442820 1.687010
Zr 0.045130 1.386070 -1.728920
Zr -0.221460 -1.940310 -1.622590 Zr -2.541940 -0.092020 0.006430
Zr -0.211420 -1.897970 1.659270
Co 1.217970 3.607720 -0.040190 H -0.540570 4.022140 -1.786900
H -0.423900 4.169400 1.867520
A-6-(S=3/2)
SCF=-4364.262672 au C -4.297590 3.026660 2.357620
C 4.211050 -2.780730 3.681870
C -4.471910 -2.649940 3.515280 C 4.354380 2.684740 2.626370
C 4.235150 -3.999570 -2.412180
C -4.242960 1.848430 -3.569270 C 4.440610 1.468840 -3.472750
C -4.435170 -3.850730 -2.403510
H -4.608360 2.497970 3.269320 H -3.952480 4.024700 2.647590
H -5.179870 3.094480 1.711360
H -5.439910 -2.670580 3.004100 H -4.252510 -3.621050 3.972620
H -4.538950 -1.916440 4.331390
H 3.824100 -3.385210 4.508330 H 4.928970 -3.365300 3.093040
H 4.768800 -1.926330 4.087660
H 4.030210 3.131290 3.572660 H 5.247850 2.067660 2.768260
H 4.612850 3.502460 1.939130
H -5.231960 1.898950 -3.102110 H -3.962150 2.821980 -3.986570
S29
H -4.301350 1.142990 -4.410290 H -4.622950 -3.363530 -3.370660
H -4.155650 -4.890390 -2.604130
H -5.366740 -3.802000 -1.829370 H 4.475220 0.867800 -4.391610
H 4.239370 2.505320 -3.773900
H 5.408800 1.399440 -2.967340 H 3.864020 -4.583780 -3.260540
H 5.076910 -3.367200 -2.717650
H 4.623060 -4.697660 -1.657590 C -3.311860 -2.195970 2.623050
C -3.185510 2.182630 1.761670
C -3.158150 1.311720 -2.651490 C 3.292860 0.985590 -2.599760
C 3.099830 -3.180190 -1.792580
C 3.072310 -2.283060 2.785540 C -3.276750 -3.085440 -1.754960
C 3.216710 1.900080 1.991090
O -1.164970 1.193070 -0.322890 O -3.533810 0.672910 -1.635700
O -3.607230 -2.058480 -1.102450
O -3.546540 1.218350 1.039810 O -1.983770 2.476570 2.055150
O 2.025320 2.258100 2.238070
O 1.856500 -2.436040 3.131140 O 3.561140 0.976130 1.203900
O 3.453540 -1.719790 1.722930
O 3.611370 0.428640 -1.511400 O 3.470390 -2.261860 -1.013600
O 1.885630 -3.458820 -2.064670
O 2.111870 1.193680 -3.005380 O 1.180850 -0.837920 -1.550920
O 1.313810 1.460210 -0.347420
O 0.144680 3.694040 0.777630
O 0.226030 3.037420 -2.345620
O 1.152480 -0.198710 1.654440
O -1.268380 -0.107880 1.882510 O -2.117040 -2.491930 2.961150
O -3.630420 -1.505450 1.618610
O -1.236610 -0.854480 -1.868240 O -1.949000 1.514160 -2.991510
O -2.078620 -3.479910 -1.942820
O 1.105110 -2.463780 0.434420 O -1.321770 -2.185770 0.351950
Zr 2.474090 -0.613060 0.082380
Zr -0.031660 1.499000 1.347300 Zr 0.002810 0.838600 -1.959820
Zr -0.075320 -2.432740 -1.260780
Zr -2.504810 -0.461580 -0.006360 Zr -0.104370 -1.792610 1.960910
Co 1.180980 3.389730 -0.752670
H -0.459450 3.576650 -2.751780 C -0.569690 4.894380 1.026930
H -1.034080 4.788810 2.023900 C 0.402840 6.054580 1.039320
H -0.098990 7.010520 1.243760
H 1.186100 5.906340 1.794660 H 0.894800 6.151190 0.053370
C -1.666290 5.061470 -0.006690
H -1.233370 5.252890 -1.003150 H -2.277910 4.151680 -0.077230
H -2.323800 5.909210 0.233180
A-TS2-3-(S=3/2)
SCF=-4364.149570
C 4.700430 0.567310 -3.286360 C -5.382040 -1.871180 -2.760660
C 2.766340 -4.877480 -2.831220
C -3.504410 3.347120 -3.256500 C -5.087130 -1.432300 3.431660
C 4.960500 1.011810 2.734760
C -3.265660 3.813050 2.941180 C 3.034420 -4.461730 3.188030
H 4.697180 -0.248210 -4.022870
H 4.687860 1.515780 -3.833660 H 5.623220 0.468040 -2.704130
S30
H 3.722180 -5.121310 -2.355900 H 2.172190 -5.783120 -2.996600
H 2.982840 -4.448170 -3.819640
H -5.330090 -2.761210 -3.395880 H -6.180510 -1.986840 -2.017140
H -5.655860 -1.003020 -3.374580
H -3.163030 3.393440 -4.296360 H -4.565890 3.084310 -3.201930
H -3.379900 4.346900 -2.816860
H 5.842070 0.580020 2.249710 H 5.085020 2.091940 2.872250
H 4.873470 0.568160 3.736560
H 3.494110 -3.851370 3.978150 H 2.440200 -5.242220 3.674910
H 3.849000 -4.901100 2.602280
H -3.393930 3.515970 3.991070 H -2.684710 4.744500 2.939080
H -4.252050 3.977210 2.496570
H -4.840440 -1.879640 4.399970 H -5.615950 -0.481880 3.568760
H -5.780150 -2.105790 2.908610
C 1.952170 -3.823120 -2.072150 C 3.447580 0.378260 -2.454190
C 3.648950 0.694930 2.036920
C -2.461070 2.748220 2.209710 C -3.823540 -1.260380 2.588310
C -4.042230 -1.612990 -2.069670
C 2.143060 -3.510220 2.374760 C -2.651980 2.368440 -2.466090
O 1.424570 0.737410 -0.143050
O 3.653130 -0.257130 1.214320 O 2.727430 -2.865000 1.462070
O 3.533610 -0.431890 -1.491020
O 2.398550 1.006490 -2.788590
O -1.465900 2.147750 -2.852170
O -2.996080 -2.257260 -2.397080
O -3.192670 1.876730 -1.434310 O -4.082230 -0.712480 -1.185060
O -3.083350 2.084530 1.334680
O -3.955640 -0.507340 1.585450 O -2.746150 -1.861110 2.905640
O -1.234530 2.608590 2.507680
O -1.249990 0.091560 1.603410 O -0.752630 1.967620 -0.139130
O 0.886180 3.195930 -1.924330
O 1.088040 3.447900 1.225330 O -1.380650 -0.147000 -1.534770
O 0.854240 -1.016610 -1.940370
O 0.694900 -3.742820 -2.277190 O 2.609520 -3.060750 -1.313070
O 1.019140 -0.722600 1.940390
O 2.632860 1.395770 2.341990 O 0.911160 -3.383040 2.682430
O -1.989230 -1.938650 0.205530 O 0.391160 -2.488180 0.142840
Zr -2.621800 0.338490 0.055670
Zr 0.325010 1.022680 -1.855860 Zr 0.470960 1.266900 1.577880
Zr -0.671410 -1.876580 1.789380
Zr 2.120780 -1.303340 -0.023030 Zr -0.807530 -2.120040 -1.480470
Co 0.253910 3.522800 -0.374680
C 3.960320 3.112520 -0.311150 H 3.343590 3.246630 -1.212880
H 3.906920 2.050550 -0.036060
H 5.006800 3.321730 -0.598320 C 3.532620 4.033750 0.790910
H 2.411410 3.670020 1.154280
H 4.081700 3.893050 1.736610 C 3.346070 5.471490 0.412840
H 2.643860 5.574210 -0.431330
H 2.976000 6.082510 1.246460 H 4.296710 5.916760 0.072510
A-TS2-3-(S=5/2) SCF=-4364.146101 au
S31
C 4.720850 0.772640 -3.217910 C -5.288360 -1.976770 -2.850160
C 2.947490 -4.735150 -2.881710
C -3.564150 3.303710 -3.231730 C -5.073810 -1.641550 3.351930
C 4.902260 1.115530 2.812720
C -3.406600 3.664180 2.975560 C 3.137800 -4.420710 3.146640
H 4.750230 -0.029120 -3.968810
H 4.685510 1.730070 -3.748360 H 5.639870 0.690610 -2.627110
H 3.905070 -4.958730 -2.399990
H 2.382830 -5.655080 -3.069910 H 3.161580 -4.281680 -3.859810
H -5.202660 -2.853180 -3.500490
H -6.090960 -2.129820 -2.117930 H -5.581660 -1.106240 -3.451610
H -3.213100 3.379110 -4.266660
H -4.617720 3.008190 -3.193900 H -3.474690 4.298650 -2.772990
H 5.801670 0.719290 2.330100
H 4.992560 2.196250 2.970810 H 4.817860 0.651390 3.805420
H 3.570260 -3.811240 3.952660
H 2.562230 -5.227390 3.612780 H 3.971580 -4.824720 2.562440
H -3.537170 3.344400 4.018480
H -2.854100 4.612550 2.996630 H -4.392640 3.806670 2.522780
H -4.824190 -2.098760 4.314870
H -5.632580 -0.710090 3.499920 H -5.740450 -2.325960 2.809150
C 2.093990 -3.719690 -2.114280
C 3.464080 0.527350 -2.405050
C 3.609510 0.771380 2.091260
C -2.566070 2.634400 2.236220
C -3.806500 -1.420740 2.523140 C -3.963330 -1.693060 -2.137690
C 2.226360 -3.485290 2.341290
C -2.687240 2.347690 -2.439670 O 1.413060 0.795070 -0.102700
O 3.652960 -0.166980 1.253550
O 2.799470 -2.810250 1.443260 O 3.563970 -0.294130 -1.454450
O 2.396610 1.125020 -2.745440
O -1.475670 2.204830 -2.789760 O -2.898060 -2.310090 -2.460160
O -3.232710 1.801890 -1.440340
O -4.034740 -0.805600 -1.242780 O -3.158340 1.966170 1.344650
O -3.945000 -0.646560 1.537910
O -2.719950 -2.009340 2.835560 O -1.338720 2.525310 2.546720
O -1.264430 0.018740 1.629130 O -0.840520 1.901730 -0.093520
O 0.858400 3.259660 -1.774550
O 0.884820 3.462760 1.353480 O -1.356030 -0.160720 -1.587250
O 0.920110 -0.954250 -1.919150
O 0.838270 -3.668350 -2.338640 O 2.718910 -2.956900 -1.329110
O 1.031160 -0.737560 1.928930
O 2.567070 1.433180 2.395740 O 0.988930 -3.399920 2.640640
O -1.925940 -1.969770 0.147070
O 0.461170 -2.494010 0.108800 Zr -2.604750 0.259060 0.036140
Zr 0.328070 1.059940 -1.815300
Zr 0.419930 1.246410 1.616060 Zr -0.628390 -1.931420 1.754510
Zr 2.161400 -1.241130 -0.012280
Zr -0.723500 -2.114530 -1.524470 Co 0.033570 3.551290 -0.304920
C 3.855700 3.188920 -0.365140
H 3.197460 3.226320 -1.248230 H 3.920770 2.140070 -0.044990
S32
H 4.861120 3.496440 -0.704540 C 3.370650 4.106790 0.716990
H 2.315740 3.726960 1.092940
H 3.935730 4.002160 1.659630 C 3.190070 5.543690 0.312710
H 2.552010 5.631100 -0.580750
H 2.748690 6.151590 1.113860 H 4.157540 6.002510 0.048660
A-TS4-5-(S=3/2) SCF=-4364.182195 au
C 2.744170 -4.436080 2.683990
C -2.464910 4.519580 3.418290 C 5.335040 0.698720 3.401500
C -4.936100 -0.429900 2.787240
C -2.081550 5.160360 -2.751490 C 3.085830 -3.805810 -3.316280
C -4.610570 0.233850 -3.388190
C 5.702710 1.342370 -2.592330 H 3.266910 -4.021120 3.557100
H 2.013100 -5.167180 3.045120
H 3.501950 -4.921850 2.059380 H 6.210600 0.266880 2.905660
H 5.557690 1.703150 3.778450
H 5.099310 0.071560 4.272810 H -1.842560 4.963990 4.201530
H -2.877100 5.306680 2.774630
H -3.325170 4.017170 3.880180 H -4.815130 -0.898210 3.770220
H -5.480240 0.516870 2.866590
H -5.530260 -1.110740 2.161340 H 3.968000 -4.235920 -2.830750
H 2.410210 -4.596760 -3.661230
H 3.422720 -3.259150 -4.208320
H 5.647710 0.748720 -3.515880
H 5.887660 2.383380 -2.877510
H 6.535720 0.946630 -2.001530 H -4.403310 0.720290 -4.351370
H -4.874190 -0.809480 -3.604980
H -5.447880 0.746940 -2.905380 H -1.513100 5.464480 -3.636380
H -3.117710 4.924360 -3.020360
H -2.122040 6.012990 -2.059440 C 4.075180 0.709230 2.528960
C 2.084430 -3.255240 2.000120
C 2.357590 -2.785620 -2.464700 C -3.346280 0.252640 -2.543030
C -1.392520 3.987180 -2.051030
C -1.669580 3.505630 2.588300 C 4.341470 1.194990 -1.899850
C -3.581330 -0.253610 2.116380
O 0.620440 -1.658230 -0.193440 O 2.985790 -2.286570 -1.498760
O 4.214940 0.177670 -1.166650 O 2.804390 -2.597950 1.199410
O 0.884300 -2.980880 2.300410
O -2.645890 -1.040670 2.440270 O -0.506710 3.135290 2.944880
O -3.525960 0.641400 1.227020
O -2.277300 3.079240 1.566200 O -3.383110 0.960140 -1.497180
O -2.105590 3.381280 -1.206000
O -0.182840 3.695270 -2.324420 O -2.369250 -0.452660 -2.927940
O -0.650500 1.072770 -1.576500
O -1.745980 -0.918370 -0.263870 O -1.638210 -3.267080 1.166290
O -1.395960 -2.893800 -2.204550
O -0.831110 0.702860 1.594180 O 1.327100 -0.374150 1.920660
O 3.122640 1.506450 2.823840
O 4.053110 -0.126520 1.586270 O 1.543050 0.048180 -1.890480
O 1.171750 -2.478570 -2.811190
O 3.422320 2.049770 -2.130750 O 0.157070 2.669900 0.263250
S33
O 2.225680 1.363510 0.237520 Zr -1.889350 1.558710 0.025450
Zr -0.494620 -1.368140 1.497380
Zr -0.292760 -0.956620 -1.891790 Zr 1.178550 2.005450 -1.403500
Zr 2.558190 -0.723610 0.035690
Zr 0.987080 1.636660 1.848010 Co -2.204220 -2.773630 -0.450410
H -0.751100 -3.590660 -2.380450
C -4.075120 -3.744790 0.160730 H -3.920530 -4.648260 -0.448690
C -4.044670 -3.914390 1.570600
H -4.175090 -4.937210 1.940510 H -2.806220 -3.694890 1.733660
H -4.529620 -3.146710 2.182570
C -4.583470 -2.561000 -0.585460 H -3.917380 -2.235240 -1.424090
H -5.499310 -2.824530 -1.142230
H -4.778460 -1.681460 0.040480
A-TS4-6-(S=3/2)
SCF=-4364.175043 au C 2.572360 -4.638260 2.451650
C -2.528820 4.335200 3.605990
C 5.210720 0.393380 3.598490 C -5.047920 -0.519300 2.561820
C -1.920570 5.377320 -2.490560
C 3.132860 -3.617170 -3.477980 C -4.496930 0.547080 -3.540780
C 5.797180 1.426950 -2.322940
H 3.070190 -4.290970 3.367790 H 1.818580 -5.379320 2.738050
H 3.344400 -5.094190 1.822040
H 6.096740 -0.019270 3.104880
H 5.434590 1.366710 4.049100
H 4.935580 -0.286150 4.417400
H -1.927870 4.716160 4.437870 H -2.906780 5.170080 3.002780
H -3.411900 3.817780 4.003770
H -4.968230 -1.053750 3.514820 H -5.580720 0.429130 2.685790
H -5.629630 -1.147040 1.871980
H 3.991170 -4.093300 -2.992630 H 2.458330 -4.372040 -3.897780
H 3.508650 -3.018280 -4.319510
H 5.765930 0.896890 -3.285450 H 6.007080 2.481330 -2.531420
H 6.603180 0.978950 -1.732000
H -4.249060 1.092800 -4.461680 H -4.767900 -0.474980 -3.835680
H -5.343090 1.041010 -3.053430
H -1.317140 5.729890 -3.333320 H -2.949990 5.177120 -2.809620
H -1.972880 6.182730 -1.744810 C 3.981620 0.482000 2.689270
C 1.954770 -3.406020 1.816980
C 2.393190 -2.636410 -2.589630 C -3.261750 0.480010 -2.654940
C -1.269820 4.152240 -1.841070
C -1.718780 3.364190 2.735640 C 4.413060 1.262370 -1.687330
C -3.678060 -0.333830 1.927760
O 0.622040 -1.641530 -0.319800 O 2.998590 -2.213480 -1.574000
O 4.246850 0.202790 -1.026290
O 2.720260 -2.705590 1.101390 O 0.741470 -3.139570 2.074700
O -2.785170 -1.195310 2.185650
O -0.569730 2.962510 3.105960 O -3.572600 0.629980 1.124550
O -2.298180 3.008420 1.671820
O -3.320390 1.120990 -1.567960 O -2.021370 3.494360 -1.073020
O -0.047720 3.876600 -2.078460
O -2.287610 -0.223910 -3.051120 O -0.579680 1.220680 -1.583960
S34
O -1.718770 -0.794640 -0.401900 O -1.645830 -3.320440 0.771030
O -1.351740 -2.716130 -2.375110
O -0.900420 0.613470 1.635540 O 1.246130 -0.513040 1.894470
O 3.027360 1.266510 3.010940
O 3.984660 -0.283680 1.689310 O 1.611570 0.172000 -1.845650
O 1.228670 -2.280390 -2.960620
O 3.518170 2.148660 -1.891650 O 0.151990 2.625430 0.424780
O 2.228280 1.334900 0.387300
Zr -1.854080 1.577910 0.040130 Zr -0.578490 -1.444870 1.324750
Zr -0.238000 -0.798470 -1.971860
Zr 1.250760 2.094200 -1.246490 Zr 2.538770 -0.746510 0.050520
Zr 0.929310 1.495770 1.971020
Co -2.340960 -2.655640 -0.767460 H -0.778010 -3.455110 -2.609630
C -3.585970 -3.852510 0.350020
H -3.365750 -4.688840 -0.333040 C -3.795330 -4.267290 1.759100
H -4.794290 -4.730130 1.845890
H -3.043370 -4.991640 2.084620 H -3.762080 -3.394150 2.423980
C -4.544980 -2.827220 -0.219120
H -4.093790 -1.842880 -0.538420 H -5.090690 -3.208220 -1.092510
H -5.261530 -2.492670 0.541710
propane
SCF=-119.033918 au
C 1.265601 -0.255455 -0.000005
H 1.318326 -0.909126 0.883936
H 2.172056 0.365639 -0.000061
H 1.318266 -0.909225 -0.883877 C -0.000025 0.578472 -0.000006
H 0.000009 1.250131 -0.875049
C -1.265591 -0.255460 -0.000001 H -1.318964 -0.908107 0.884641
H -1.317535 -0.910239 -0.883160
H 0.000014 1.250013 0.875137 H -2.172077 0.365576 -0.001492
propene SCF=-117.799298 au
C 1.227291 0.162508 0.000011
H 1.812166 -0.151281 0.878640 H 1.183657 1.259939 -0.000862
H 1.812917 -0.152698 -0.877602
C -0.127190 -0.450508 -0.000094 H -0.158878 -1.548044 0.000208
C -1.282278 0.217632 -0.000028 H -1.311570 1.311957 0.000111
H -2.245229 -0.297666 0.000175
S35
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