Supporting Information
Improving Singlet Oxygen Resistance during Photochemical Water
Oxidation by Cobalt Porphyrin Catalysts
Takashi Nakazono,[a, b] Alexander R. Parent,[b] and Ken Sakai*[a, b, c]
chem_201500716_sm_miscellaneous_information.pdf
Supplementary Information
Improving Singlet Oxygen Resistance during Photochemical Water
Oxidation by Cobalt Porphyrin Catalysts
Takashi Nakazono,a,b Alexander Rene Parent,b and Ken Sakaia,b,c*
a
Department of Chemistry, Faculty of Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-
ku, Fukuoka 812-8581, Japan
b
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu
University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan
c
Center for Molecular Systems (CMS), Kyushu University, Motooka 744, Nishi-ku, Fukuoka
819-0395, Japan
1
Materials
All solvents and reagents were of the highest quality available and were used as received. 2,6-difluoro
benzaldehyde and pyrrole were purchased from TCI Fine Chemicals Co., were used as received.
[Ru(bpy)3](NO3)2·3H2O was prepared as previously described.1
Synthesis
Na3[diaqua-(5,10,15,20-tetra(2,6-difluoro-3-sulfophenyl)porphyrinato)cobalt(III)] •14H2O (CoFPS)
5,10,15,20-tetra(2,6-difluoro-3-sulfophenyl)porphyrin (FPS) was synthesized based on literature
methods.2 Co(CH3COO)2·4H2O (0.15 g, 6 mmol), tetra(2,6-difluoro-3-sulfophenyl)porphyrin (0.11 g, 1
mmol) were added to water (25 mL). The pH was adjusted to 7.5 by addition of 1 M NaOH. The solution
was refluxed for 24 h, then passed through the Na+ form of the cation-exchange resin Dowex 50W-X8
(50-100-mesh) to remove excess Co2+. The CoFPS was then precipitated from solution via the addition of
acetone (25 mL x 4). The precipitate was collected by filtration, washed with acetone and diethyl ether,
and dried in vacuum. Yield 0.14 g (0.94 mmol, 94 %).
Elemental analysis of CoFPS calcd. (%) for C44H20N4O14S4Na3Co·14H2O (1489.0): C 35.49, H 3.25, N
3.76. Found: C 35.55, H 3.47, N 3.61.
ESI-TOF MS: m/z 376.93 [M–3Na–2H2O]3– (Calcd.: 376.96 m/z); m/z 382.91 [M–3Na–H2O]3– (Calcd.:
382.92 m/z); 576.89 [M–2Na–2H2O]2– (Calcd.: 576.96 m/z) ; 585.87 [M–2Na–H2O]2– (Calcd.: 585.95
m/z); 1176.87 [M–Na–2H2O]– (Calcd.: 1176.76 m/z).
1
H-NMR (600.13 MHz, D2O): δ ppm 7.30 (m, 8H), 6.23-6.20 (m, 4H), 5.50-4.48 (m, 4H).
Oxygen Production
Photochemical oxygen production from water was analyzed by using an automatic GC H2/O2 monitoring
system developed in our group. In this system, continuous flow of Ar (10.0 mL/min, controlled by a
STEC SEC-E40/PAC-D2 digital mass flow controller) is bubbled through a photolysis solution (10 mL)
contained in a Pyrex vial (ca. 20 mL). The vent gas from the vial is introduced into a valve which allows
the automatic injection of the sample gas onto the GC (Shimadzu GC-8A equipped with a molecular sieve
5 Å column of 2 m × 3 mm i.d., at 30 ºC). The injection of the sample gas is controlled by software
developed by Prof. Ken Sakai, and the output signal from the thermal conductivity detector of the gas
chromatograph is analyzed by the Shimadzu C-R8A integrator. Photolysis solutions were degassed with
Ar for at least 30 min prior to photolysis. Photoirradiation was performed using an ILC Technology
CERMAX LX-300 300 W Xe lamp equipped with a CM-1 cold mirror (400 < λ < 800 nm). The
photolysis vial is immersed in a 20 ºC water bath to remove IR radiation and to eliminate temperature
effects.
Procedure for Electrochemical Measurements
Square wave voltammograms were recorded on a BAS ALS Model 750C electrochemical analyzer, using
a three electrode system consisting of a platinum working electrode, a platinum wire counter electrode,
and a Ag/Ag+ reference electrode, where TBAP (tetra(n-butyl)ammonium perchlorate) was used as a
supporting electrolyte.
General Procedure for Dynamic Light Scattering Analysis
Dynamic light scattering (DLS) experiments were carried out using a ELSZ-2 (Otsuka Electronics Co.
Ltd. Japan). A He laser operating at 660 nm was used. The DLS measurements were carried out for a 100
2
mM borate buffer solution at pH = 9 containing 10 µM catalyst, 0.2 mM [Ru(bpy)3](NO3)2, and 7.0 mM
Na2S2O8.
DFT Calculations
DFT Calculations were performed in Gaussian 09 using the CAM-B3LYP functional with the 6-31**
basis set for H, C, N, O and F, and the LanL2DZ basis set for Co and S. Structures were optimized using
the polarizable continuum model for solvent water unless noted otherwise. Figures were made using
GaussView 5.09 and Mercury 3.1.
3
Figure S1. Photochemical O2 production for the first run and second run from an aqueous borate buffer
solution (100 mM, pH = 9.0; 10 mL) containing [Ru(bpy)3](NO3)2 (0.2 mM), Na2S2O8 (3.0 mM) and
either CoFPS (6 M) (a) or CoTPPS (6 M) (b) under Ar at 20 °C. A 300 W Xe (400 < < 800nm)
light source with the light intensity reduced to 1% using neutral density filters. After the completion of
the first run, an additional 3.0 mM of Na2S2O8 was added to the reaction solution.
4
Figure S2. UV-VIS spectral time-course upon photoirradiation of a (1:1) THF/aqueous borate buffer (100
mM, pH 9) solution containing DPA (0.125 mM), CoFPS (1 M), [Ru(bpy)3](NO3)2 (10 M) and
Na2S2O8 (1.0 mM). (a) Light source: 410-800 nm (b) Light source: 430-510 nm under air at 20 °C. (c)
The reaction scheme of DPA and singlet oxygen.
5
Figure S3. UV-VIS spectral time-course upon photoirradiation of a (1:1) THF/aqueous borate buffer (100
mM, pH 9) solution containing containing (a) DPA (0.125 mM), (b) DPA (0.125 mM) and CoFPS (1
M), (c) DPA (0.125 mM) and [Ru(bpy)3](NO3)2 (10 M) under air at 20 °C. (Light source: 410-800 nm).
6
Figure S4. Light scattering intensity as a function of time during photo-irradiation of an aqueous catalyst
solution. (●, [Co(bpy)3](PF6)2 (10 µM) in 100 mM pH 11 phosphate buffer containing Na2S2O8 (5.0 mM)
and [Ru(bpy)3](NO3)2 (1.0 mM); ◆, CoFPS in 100 mM pH 9 borate buffer containing Na2S2O8 (7.0 mM)
and [Ru(bpy)3](NO3)2 (0.2 mM) under Ar. Data for [Co(bpy)3](PF6)2 previously reported in Ref. 17 of the
main text. (Light source: 400-800 nm).
7
Figure S5. Autocorrelation function obtained by DLS measurements of (a-e) CoFPS (10 µM) in a 100
mM pH 9 borate buffer containing Na2S2O8 (7.0 mM) and [Ru(bpy)3](NO3)2 (0.2 mM) and (f) [Co(bpy)3]
(PF6)2 (10 µM) in 100 mM pH 11 phosphate buffer containing Na2S2O8 (5.0 mM) and [Ru(bpy)3](NO3)2
(1.0 mM) under Ar atmosphere. Data for [Co(bpy)3](PF6)2 previously reported in Ref. 17 of the main text.
(Light source: 400-800 nm).
8
Figure S6. (a) Photo-initiated O2 production by CoFPS (10 M) at various concentrations of
[Ru(bpy)3](NO3)2 in 100 mM pH 9 borate buffer containing Na2S2O8 (3.0 mM). ([Ru(bpy)3](NO3)2: ●,
0.1 mM; ■, 0.2 mM ;◆, 0.3 mM; ▲, 0.5 mM; ▼, 1.0 mM) under Ar at 20 °C. (b) Initial rate of O2
evolution as a function of the concentration of [Ru(bpy)3](NO3)2. (Light source: 400-800 nm).
9
Figure S7. Initial rate of photo-initiated O2 production (red) and TON (blue) vs. light intensity (400-800
nm) adjusted with neutral density filters. Reaction conditions: 100 mM pH 9 borate buffer solution
containing CoFPS (6 M), Na2S2O8 (3.0 mM), and [Ru(bpy)3](NO3)2 (0.2 mM) under Ar at 20 °C.
10
Figure S8. Photochemical O2 production at various pH. Solution conditions: 100 mM (B basis) borate, 6
µM CoFPS, 3.0 mM Na2S2O8, and 0.2 mM [Ru(bpy)3](NO3)2 under Ar at 20 °C. (Light source: 400-800
nm).
11
Figure S9. Calculated spin-density for high-spin [CoIV(O•)(FPS)]3− (top) and [CoIV(O•)(TPPS)]3− (bottom).
12
Figure S10. Photo-initiated O2 production from an aqueous CoFPS solution in 100 mM pH 9 borate
buffer containing 7.0 mM Na2S2O8 and 0.2 mM [Ru(bpy)3](NO3)2 (catalyst concentration: ●, 1.0 µM; ■,
2.0 µM; ◆, 3.2 M; ▲, 4.7 M; ▼, 6.0 µM.) under Ar at 20 °C. (Light source: 430-510 nm).
13
Figure S11. (a) Photo-initiated O2 production from an aqueous CoTPPS solution in 100 mM pH 9 borate
buffer containing 7.0 mM Na2S2O8 and 0.2 mM [Ru(bpy)3](NO3)2 under Ar at 20 °C. (b) Initial WO rate
(blue) and TOF (red) vs. [CoTPPS] upon irradiation between 430 and 510 nm.
14
Figure S12. Square wave voltammograms of (a) 1.0 mM CoFPS and (b) 1.0 mM CoTPPS in 100 mM
TBAP DMF solution under Ar at 20 °C. The blue line indicates the blank electrode response. (P =
porphyrin ligand)
15
e.
f.
Figure S13. DFT optimized geometries for low-spin [CoIII(OH2)(FPS)]3−.
16
Table S1. Relative energy of low-spin [CoIII(OH2)(FPS)]3− conformations calculated by DFT.
Structure
Zero-Point
Sum of Electronic and Zero- Electronic Energy Relative Energy
Correction (Hartree)
Point Energy (Hartree)
(Hartree)
(kJ/mol)
0.573143
-3866.096179
-3866.201769
1.65
CoFPS a
0.573389
-3866.095909
-3866.200926
3.87
CoFPS b
0.573042
-3866.095791
-3866.201171
3.23
CoFPS c
0.573333
-3866.096424
-3866.200457
5.10
CoFPS d
0.573288
-3866.096502
-3866.202107
0.77
CoFPS e
0.573086
-3866.096414
-3866.202401
0
CoFPS f
Table S2. DFT calculated Cartesian coordinates and charge densities for [CoIII(OH2)(FPS)]3− a.
Co 1
Atom
x
0.152864
y
-0.05048
z
-0.65404
Charge Density
0.762234
N 2
-1.62996
-0.83074
-0.80897
-0.60983
N 3
1.938401 0.721374
-0.78317
-0.59855
N 4
-0.61366
1.729073
-0.84304
-0.59905
N 5
0.921699
-1.84327
-0.72344
-0.60863
C 6
-3.89268
-1.12985
-1.13758
-0.11168
C 7
0.276211
-3.02359
-0.42392
0.263215
C 8
-2.80675
-0.19394
-1.13499
0.279174
C 9
-1.97917
-2.13655
-0.56169
0.266597
C 10
2.415959
-3.5994
-0.73386
-0.11192
C 11
2.277737 2.030054
-0.53775
0.278687
C 12
3.12949
0.069727
-1.00114
0.278675
C 13
-1.09509
-3.17341
-0.29459
0.030781
C 14
-0.90503
4.009014
-0.65684
-0.11087
C 15
2.240054
-2.1862
-0.9031
0.277045
C 16
0.018946 2.916107
-0.56471
0.27833
C 17
4.221419 1.000233
-0.95058
-0.11474
C 18
-2.95629
1.170671
-1.32987
0.027802
C 19
-2.09492
3.485319
-1.0275
-0.11074
C 20
-1.919
2.064095
-1.10795
0.272854
C 21
-3.38867
-2.32071
-0.7438
-0.11214
C 22
1.210513
-4.11034
-0.39851
-0.11113
C 23
3.70005
2.200662
-0.61695
-0.11111
C 24
3.287952
-1.30226
-1.11679
0.025349
17
C 25
1.381183 3.071815
-0.35631
0.022361
O 26
0.134856
0.0659
1.230539
-0.5211
C 27
4.639717
-1.86098
-1.38724
-0.20856
C 28
7.175056
-2.92928
-1.94064
-0.01597
C 29
4.940475
-2.46068
-2.60915
0.396096
C 30
5.665021
-1.82939
-0.44926
0.480421
C 31
6.920674
-2.3462
-0.71125
-0.44665
C 32
6.180511
-2.99508
-2.90733
-0.15454
C 33
1.896646 4.427821
-0.02587
-0.21236
C 34
2.836713 6.992381 0.612585
-0.01582
C 35
1.729469 4.970377 1.242878
0.483864
C 36
2.550816 5.229016
-0.95915
0.395813
C 37
3.025334 6.495445
-0.67031
-0.15426
C 38
2.189435 6.232423
1.57153
-0.44587
C 39
-4.2864
1.710703
-1.71776
-0.20613
C 40
-6.78026
2.728896
-2.50566
-0.01562
C 41
-5.38023
1.70514
-0.8599
0.479382
C 42
-4.49755
2.259442
-2.98204
0.396062
C 43
-5.71479
2.768753
-3.395
-0.15443
C 44
-6.61616
2.19704
-1.23832
-0.44698
C 45
-1.65592
-4.50907
0.042497
-0.20905
C 46
-2.7585
-7.00715
0.687811
-0.01575
C 47
-1.64959
-5.57467
-0.85554
0.395607
C 48
-2.24246
-4.75007
1.279691
0.48286
C 49
-2.78992
-5.97589
1.610605
-0.44573
C 50
-2.18407
-6.81591
-0.56192
-0.15414
H 51
-4.91435
-0.89642
-1.39392
0.143207
H 52
3.356891
-4.12033
-0.82412
0.144001
H 53
-0.65678
5.046281
-0.49124
0.14354
H 54
5.257617 0.753063
-1.1215
0.143041
H 55
-3.025
4.00426
-1.20231
0.143583
H 56
-3.91172
-3.25716
-0.62421
0.144577
H 57
0.965201
-5.13586
-0.1696
0.143341
18
H 58
4.224743 3.130283
-0.45994
0.142462
H 59
3.186359 7.977967 0.896968
0.154464
H 60
8.167552
-3.32652
-2.11844
0.154453
H 61
-3.19554
-7.95699
0.973232
0.154793
H 62
-7.7596
3.107076
-2.77468
0.154506
F 63
3.970725
-2.51687
-3.53143
-0.29554
F 64
5.41129
-1.27166
0.740052
-0.28469
F 65
2.725891 4.734989
-2.19229
-0.29727
F 66
1.098628 4.231189 2.161819
-0.28235
F 67
-3.46117
2.288435
-3.83024
-0.29579
F 68
-5.21473
1.197788 0.366956
-0.28463
F 69
-2.26964
-3.74832
2.165456
-0.28267
F 70
-1.09596
-5.3747
-2.05902
-0.29685
H 71
-0.76947
0.009073 1.581223
0.417018
H 72
0.649387
-0.64672
1.6443
0.415748
H 73
3.525883 7.069531
-1.44002
0.143521
S 74
1.952463 6.910365 3.260154
1.754681
O 75
2.612233 8.310003 3.195132
-0.86424
O 76
2.682465 5.929973 4.207839
-0.85712
O 77
0.421877 6.961321 3.476941
-0.85697
H 78
-2.14926
-7.60392
-1.30382
0.143652
S 79
-3.55486
-6.25124
3.255503
1.754746
O 80
-2.42115
-6.02992
4.284269
-0.85702
O 81
-4.0522
-7.71652
3.193813
-0.86413
O 82
-4.69936
-5.21603
3.359121
-0.85684
H 83
6.351839
-3.44549
-3.87705
0.143386
S 84
8.253856
-2.2602
0.54648
1.75506
O 85
7.737238
-3.06557
1.76159
-0.85679
O 86
8.448659
-0.75315
0.835974
-0.85731
O 87
9.469991
-2.9154
-0.15376
-0.86408
H 88
-5.81448
3.178951
-4.39218
0.143446
S 89
-8.04446
2.136398
-0.0884
1.755277
O 90
-8.25705
0.635598 0.221065
19
-0.85708
O 91
-7.62784
2.972834 1.143689
-0.85692
O 92
-9.20284
2.768521
-0.86408
-0.89896
SCF Done: E(UCAM-B3LYP) = -3866.66932165 A.U. after 1 cycles
1
2
3
A
A
A
Frequencies -6.5260
7.3284
12.9276
Red. masses -- 14.8820
13.8118
15.9441
Zero-point correction = 0.573143 (Hartree/Particle)
Thermal correction to Energy = 0.635475
Thermal correction to Enthalpy = 0.636419
Thermal correction to Gibbs Free Energy = 0.467553
Sum of electronic and zero-point Energies = -3866.096179
Sum of electronic and thermal Energies = -3866.033847
Sum of electronic and thermal Enthalpies = -3866.032903
Sum of electronic and thermal Free Energies = -3866.201769
Item Value Threshold Converged ?
Maximum Force
0.000046 0.000450 YES
RMS Force
0.000004 0.000300 YES
Table S3. DFT calculated Cartesian coordinates and charge densities for [CoIII(OH2)(FPS)]3− b.
Co
N
N
N
N
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
Atom
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
x
-0.1471
0.243597
-0.48081
-2.00771
1.762517
0.0856
2.71788
-0.58716
1.397915
3.780429
-1.70427
0.44177
2.549674
-4.30085
2.405863
-3.05325
-0.22171
-1.91855
-4.00811
-2.58479
1.297418
y
-0.07173
1.835619
-1.94267
0.340374
-0.45395
4.13569
0.372883
2.892428
2.407286
-1.55827
-2.56683
-2.94023
1.723969
0.137577
-1.64575
-0.55136
-4.19112
2.791886
1.449949
1.575972
3.836568
z
-0.38001
-0.51652
0.063893
0.033892
-0.55343
-0.45161
-1.10323
-0.21449
-0.99594
-0.71947
0.096116
0.275825
-1.36217
0.18478
-0.32055
0.025822
0.508947
0.157634
0.321839
0.194855
-0.96984
20
Charge Density
0.76259
-0.61211
-0.59962
-0.59787
-0.60763
-0.11276
0.263098
0.278902
0.266081
-0.11151
0.27838
0.280396
0.032277
-0.11117
0.278223
0.279681
-0.11515
0.030192
-0.11057
0.273788
-0.11166
C
C
C
C
O
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
F
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
3.963129
-1.54497
1.814872
-2.93284
-0.53245
2.684393
4.339416
3.479828
2.759524
3.566077
4.298569
-4.1724
-6.51495
-4.88905
-4.68297
-5.83525
-6.04459
-2.69148
-4.17514
-3.03024
-3.13684
-3.86682
-3.75731
3.664537
5.740648
4.846943
3.567858
4.575075
5.879477
-0.32766
4.499862
-5.27007
0.273059
-4.69163
2.077947
4.866424
-2.35083
-7.42233
4.989761
6.565276
-4.74951
3.437153
-0.32444
-3.96906
-2.81014
-1.93192
-0.3216
-3.98525
-6.18542
-4.03759
-5.08143
-6.17846
-5.11669
-2.75427
-4.29339
-2.91968
-3.391
-4.15551
-3.67705
4.030993
6.34954
4.946354
4.326242
5.465561
6.097116
2.496364
3.966796
2.766848
3.004035
3.731111
3.485461
5.112474
-2.35863
-0.33612
-5.12236
2.272045
4.517686
0.090001
-4.68289
-4.88117
-7.01764
4.527618
7.233664
-2.99959
-1.23948
0.353058
0.146841
0.000762
-2.21174
0.424769
0.96336
1.563522
-0.43206
-0.19007
1.842103
-0.03756
-0.12988
-1.21665
1.091287
1.073236
-1.27666
0.439184
0.987934
-0.55584
1.723031
2.007514
-0.31194
-1.97196
-3.15706
-1.29265
-3.26671
-3.87402
-1.86669
-0.25365
-0.63739
0.219825
0.737471
0.469083
-1.27258
-1.65934
0.426149
-0.20504
1.206486
-3.5814
1.238798
2.405436
21
-0.11137
-0.10996
0.023831
0.020702
-0.52135
-0.21649
-0.01575
0.484048
0.39663
-0.15408
-0.44627
-0.21563
-0.01579
0.485142
0.39697
-0.15446
-0.44589
-0.2098
-0.01574
0.39563
0.480743
-0.44628
-0.15399
-0.20498
-0.01576
0.480142
0.39604
-0.15408
-0.4468
0.143408
0.144476
0.143978
0.143147
0.14352
0.144322
0.143682
0.142363
0.15447
0.154567
0.154713
0.154691
-0.28198
F 64
2.006108 -5.06086 -1.53981
-0.2969
F 65
-4.01187 -3.2523 2.242367
-0.29645
F 66
-4.42854 -2.31809 -2.31912
-0.28272
F 67
-2.84194 3.464288 2.702107
-0.28285
F 68
-2.62577 4.689231 -1.80705
-0.29721
F 69
2.437277 2.76902 -3.94585
-0.29594
F 70
4.973523 2.306444 -0.04318
-0.28419
H 71
3.580975 -6.99981 -0.89556
0.143468
H 72
-3.98846 6.768526 -1.12945
0.143588
S 73
-4.44203 5.81273 3.715014
1.754715
S 74
5.321759 -5.15356 3.364679
1.754512
O 75
4.318683 -5.07935 4.539693
-0.85721
O 76
6.068685 -6.50738 3.277721
-0.86445
O 77
6.258668 -3.92675 3.269074
-0.85691
O 78
-3.16287 5.894635 4.580675
-0.85697
O 79
-5.36882 4.631151 4.086389
-0.85708
O 80
-5.18737 7.164139 3.588107
-0.86429
H 81
4.439428 4.095798 -4.88455
0.143734
S 82
7.432007 3.800217 -0.94072
1.755406
O 83
7.015018 4.601335 0.314823
-0.85684
O 84
8.011988 2.401949 -0.62267
-0.8568
O 85
8.298128 4.615349 -1.93261
-0.86406
H 86
-0.66286 0.528331 -2.66373
0.416464
H 87
0.186871 -0.78379 -2.67271
0.415458
H 88
-6.18203 -4.62554 1.985062
0.143752
S 89
-6.95138 -3.8869 -2.85787
1.754417
O 90
-8.15958 -4.7781 -2.47845
-0.86419
O 91
-5.9539 -4.57835 -3.81693
-0.85744
O 92
-7.3543 -2.46137 -3.30276
-0.85733
SCF Done: E(UCAM-B3LYP) = -3866.66929875 A.U. after 1 cycles
1
2
3
A
A
A
Frequencies -6.2821
10.8475
12.8284
Red. masses -- 13.7665
15.1294
15.7447
Zero-point correction = 0.573389 (Hartree/Particle)
Thermal correction to Energy = 0.635599
Thermal correction to Enthalpy = 0.636543
Thermal correction to Gibbs Free Energy = 0.468373
Sum of electronic and zero-point Energies = -3866.095909
Sum of electronic and thermal Energies = -3866.033700
Sum of electronic and thermal Enthalpies = -3866.032756
Sum of electronic and thermal Free Energies = -3866.200926
Item Value Threshold Converged ?
22
Maximum Force
RMS Force
0.000005
0.000001
0.000450
0.000300
YES
YES
Table S4. DFT calculated Cartesian coordinates and charge densities for [CoIII(OH2)(FPS)]3− c.
Co
N
N
N
N
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
C
C
C
C
Atom
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
x
-0.0485
0.746877
-0.84017
-1.82512
1.737911
1.058958
2.929197
0.114135
2.06056
3.478786
-2.14855
-0.20068
3.093631
-4.10031
2.065062
-3.0141
-1.13818
-1.25241
-3.57071
-2.15195
2.254079
4.006909
-2.33032
1.167868
-3.18003
-0.12947
1.708741
2.752969
2.272686
1.69917
2.204353
2.789353
-4.53334
-7.08397
-5.07162
-5.3353
-6.59144
y
0.130453
1.908117
-1.64733
0.915357
-0.65419
4.173624
-0.02216
3.096077
2.242472
-2.16599
-1.97821
-2.84258
1.346739
1.222752
-1.97518
0.288829
-3.92765
3.263148
2.415101
2.228921
3.652643
-0.96767
-3.39932
-3.01411
-1.07365
0.128907
-4.37564
-6.93094
-4.70457
-5.38191
-6.6498
-5.96046
-1.57505
-2.49705
-1.35092
-2.27533
-2.73999
z
-0.75869
-0.61206
-0.62675
-0.60451
-0.65492
-0.31542
-0.94025
-0.32072
-0.83786
-0.61058
-0.88738
-0.39613
-1.0799
-0.82167
-0.46429
-0.88714
-0.45463
-0.15961
-0.46871
-0.36926
-0.67284
-0.94383
-0.8055
-0.26392
-1.08805
-2.64605
-0.00415
0.498521
1.223354
-0.96809
-0.7457
1.484862
-1.44789
-2.16916
-2.71402
-0.55453
-0.89858
23
Charge Density
0.763909
-0.61079
-0.59915
-0.59871
-0.60822
-0.1125
0.262939
0.278983
0.264951
-0.11197
0.276417
0.279423
0.03179
-0.11104
0.277758
0.277282
-0.11543
0.028561
-0.11091
0.274166
-0.11227
-0.11047
-0.11012
0.025546
0.024707
-0.52112
-0.21289
-0.01568
0.482173
0.396082
-0.15398
-0.44622
-0.20549
-0.01592
0.396228
0.479913
-0.44715
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
F
F
F
F
F
F
F
F
H
H
S
S
O
O
O
O
O
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
-6.32519
-1.78941
-2.84681
-1.78263
-2.35343
-2.87914
-2.29406
4.435648
6.952591
5.507029
4.681247
5.910794
6.753726
0.827649
3.989395
-5.13821
-0.9004
-4.08453
3.198696
5.039256
-3.26155
-8.07134
3.164425
7.939575
-3.26628
2.309012
1.169541
-4.85602
-4.32764
-2.38299
-1.25228
3.667011
5.307977
2.166742
-2.25948
-3.62353
3.529206
2.404266
3.948352
4.727535
-2.48655
-4.78722
-1.79313
4.613983
7.142659
5.658119
4.89275
6.13363
6.913824
1.891073
2.929209
1.845694
2.48945
3.008967
2.347726
5.200209
-3.11094
0.979215
-4.96406
3.351561
4.164344
-0.73518
-3.9192
-2.87242
-7.90626
3.314468
8.105075
-3.7596
-5.09579
-2.50396
-0.6706
3.912392
5.422153
2.557766
1.290252
-7.38875
7.683548
6.455957
-6.35473
-6.12299
-7.83996
-5.38951
6.232604
5.445615
-3.09484
0.155588
0.758085
-0.76733
1.395503
1.705117
-0.49505
-1.41732
-2.09843
-0.53265
-2.6523
-3.01295
-0.85818
-0.077
-0.50508
-0.98983
-0.27218
-0.31441
-0.77634
-1.15421
-0.96771
-2.41152
0.730788
-2.32635
1.02714
2.16882
-2.16529
0.67337
-3.59644
2.304413
-1.975
-3.52499
0.66773
-1.53637
-1.25593
3.35107
3.117229
4.152994
2.985415
3.273511
4.375596
3.483122
24
-0.15428
-0.21145
-0.01596
0.396273
0.481518
-0.44639
-0.15428
-0.20417
-0.01585
0.479828
0.396144
-0.15416
-0.44696
0.143167
0.14441
0.143374
0.143327
0.143456
0.144213
0.143448
0.142285
0.154392
0.154514
0.154493
0.15461
-0.28218
-0.2975
-0.28488
-0.29599
-0.28239
-0.29737
-0.29616
-0.28407
0.143305
0.143347
1.754882
1.754685
-0.85726
-0.86437
-0.85664
-0.85691
-0.85702
O 80
-4.09271
7.92933
3.264298
-0.8643
H 81
6.037884 3.458466
-3.98986
0.143626
H 82
-6.68551
-1.5886
-4.09529
0.143452
S 83
-7.60113
-3.6937
0.300529
1.755388
S 84
8.148353 2.238462
0.329125
1.75563
O 85
-7.80151
-2.76204
1.518488
-0.85662
O 86
-6.77106
-4.96052
0.616042
-0.85704
O 87
-8.91086
-3.99214
-0.47016
-0.86415
O 88
7.695463 3.026069
1.580585
-0.85678
O 89
8.351476 0.726379
0.584537
-0.85688
O 90
9.330169 2.900831
-0.42134
-0.86412
H 91
-0.00589 1.022084
-3.00803
0.416082
H 92
0.558285 -0.43576
-3.03556
0.415494
SCF Done: E(UCAM-B3LYP) = -3866.66883251 A.U. after 2 cycles
1
2
3
A
A
A
Frequencies --
5.2454
11.2782
12.7701
Red. masses --
13.7801
16.8006
15.2630
Zero-point correction = 0.573042 (Hartree/Particle)
Thermal correction to Energy = 0.635442
Thermal correction to Enthalpy = 0.636386
Thermal correction to Gibbs Free Energy = 0.467661
Sum of electronic and zero-point Energies = -3866.095791
Sum of electronic and thermal Energies = -3866.033390
Sum of electronic and thermal Enthalpies = -3866.032446
Sum of electronic and thermal Free Energies = -3866.201171
Item Value Threshold Converged?
Maximum Force
0.000003
0.000450
YES
RMS
0.000000
0.000300
YES
Force
25
Table S5. DFT calculated Cartesian coordinates and charge densities for [CoIII(OH2)(FPS)]3− d.
Co
N
N
N
N
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
C
C
Atom
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
x
0.092242
-0.01021
0.201493
-1.84727
2.041838
-0.75839
2.803665
-1.10866
1.002199
4.280817
-0.82212
1.324165
2.324239
-4.01742
2.941852
-2.62661
0.981586
-2.39748
-4.08112
-2.73131
0.535674
4.192584
-0.33508
2.625071
-2.15813
-0.01983
3.738861
5.870121
4.456401
4.14099
5.185281
5.50902
-3.14455
-5.03252
-3.73629
y
-0.09076
1.853602
-2.03814
-0.20636
0.025226
4.000307
1.142645
2.611234
2.757615
-0.5252
-2.9234
-2.81576
2.440173
-0.96703
-1.00719
-1.30179
-4.20726
2.131322
0.328967
0.807633
4.09435
0.795252
-4.27244
-2.34787
-2.58737
-0.07817
-3.31953
-5.11586
-3.39265
-4.18331
-5.07973
-4.2725
-3.6523
-5.62994
-3.72267
z
-0.04062
0.160132
0.037752
0.152189
0.012346
0.54756
-0.2554
0.50014
-0.05271
-0.04964
-0.20206
0.200686
-0.33229
-0.02713
0.126733
-0.1291
0.124414
0.673408
0.350752
0.430584
0.1688
-0.32216
-0.1681
0.29009
-0.35451
-1.92526
0.460665
0.786308
1.649032
-0.55641
-0.42115
1.822835
-0.68113
-1.30956
-1.93689
26
Charge Density
0.764177
-0.61045
-0.59999
-0.59929
-0.60942
-0.11223
0.263587
0.279357
0.266413
-0.11182
0.278487
0.278714
0.032537
-0.11112
0.277094
0.278477
-0.11522
0.028769
-0.11061
0.27401
-0.11216
-0.11071
-0.11037
0.027096
0.02386
-0.52065
-0.21323
-0.01608
0.481457
0.396869
-0.15405
-0.44612
-0.2129
-0.01567
0.483243
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
F
F
F
F
F
F
F
F
H
H
S
S
O
O
O
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
-3.54357
-4.47017
-4.66839
-3.48056
-5.53562
-3.96455
-4.07874
-5.09015
-4.97379
3.267516
5.029937
4.245846
3.205532
4.070395
5.127173
-1.42692
5.169246
-4.83404
1.673328
-4.96137
1.140824
4.995868
-0.93587
-5.76487
6.69865
5.694661
-6.32964
4.104579
3.475276
-2.99261
-3.38042
-3.648
-3.41603
2.271245
4.328949
5.449211
-5.30581
-5.85835
6.431122
5.391036
7.514949
7.010635
-4.61443
-5.60087
-4.69166
3.076925
4.839871
4.05445
3.016771
3.880723
4.936869
3.54795
5.646106
3.973611
4.227412
5.259951
5.00375
4.79973
-1.13619
-1.65319
-5.02462
0.92566
4.983945
1.482956
-5.15424
-6.37812
-5.7952
6.458134
5.503608
-2.57158
-4.13421
-4.57314
-2.81094
2.083644
4.135718
3.852851
3.344766
-5.72461
5.674612
3.760911
-4.33427
-4.73624
-5.41383
-2.91413
0.244267
-0.04022
-2.25993
1.053962
1.792292
0.186565
2.307903
2.685393
0.52619
-0.64052
-1.24446
0.25611
-1.85204
-2.16437
-0.01723
0.826905
-0.00438
-0.19182
0.25662
0.535089
0.083684
-0.53629
-0.3276
-1.58963
0.949213
-1.51521
2.114087
2.644217
-1.71814
1.464773
-2.84859
3.163829
-1.03306
-2.73299
1.435956
-1.25005
-0.19358
4.347313
3.408031
4.479991
3.16613
3.607043
27
0.396166
-0.15439
-0.44607
-0.21037
-0.01579
0.395511
0.481462
-0.4463
-0.15407
-0.20871
-0.01561
0.394907
0.482628
-0.44578
-0.15405
0.143196
0.144184
0.143774
0.143168
0.143603
0.144256
0.143483
0.142098
0.154533
0.154401
0.154769
0.154595
-0.28262
-0.297
-0.29689
-0.28284
-0.28293
-0.29696
-0.28331
-0.29643
0.143602
0.143712
1.754571
1.754543
-0.85696
-0.86436
-0.8574
O 78
-4.70233 3.94835 5.357529
-0.8576
O 79
-6.51017 2.359051 4.400847
-0.85678
O 80
-6.88576 4.919531 4.366516
-0.86421
H 81
-0.35353 0.771811 -2.25706
0.416814
H 82
0.847378 -0.22601 -2.33725
0.415369
H 83
-4.73903 -6.32052 0.722947
0.143745
S 84
-5.422
-4.75307 -3.93166
1.754353
O 85
-6.40358 -5.94825 -3.85257
-0.86418
O 86
-4.24631 -4.98678 -4.90957
-0.85711
O 87
-6.12588 -3.38902 -4.12244
-0.85722
H 88
5.865534 5.288159 0.722039
0.143958
S 89
3.960073 6.125099 -3.77884
1.754844
O 90
4.156945 5.029018 -4.85206
-0.85781
O 91
5.117819 7.152324 -3.72931
-0.8639
O 92
2.557729 6.777241 -3.80626
-0.85667
SCF Done: E(UCAM-B3LYP) = -3866.66975753 A.U. after 1 cycles
1
2
3
A
A
A
Frequencies --
6.0843
12.4881
13.0969
Red. masses --
13.9288
16.4249
13.3868
Zero-point correction = 0.573333 (Hartree/Particle)
Thermal correction to Energy = 0.635539
Thermal correction to Enthalpy = 0.636483
Thermal correction to Gibbs Free Energy = 0.469301
Sum of electronic and zero-point Energies = -3866.096424
Sum of electronic and thermal Energies = -3866.034219
Sum of electronic and thermal Enthalpies = -3866.033275
Sum of electronic and thermal Free Energies = -3866.200457
Item Value Threshold Converged?
Maximum Force
0.000022
0.000450
YES
RMS Force
0.000002
0.000300
YES
28
Table S6. DFT calculated Cartesian coordinates and charge densities for [CoIII(OH2)(FPS)]3− e.
Co
N
N
N
N
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
C
Atom
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
x
-0.03017
-0.05927
0.002475
-1.97586
1.921415
-0.73809
2.735718
-1.13905
0.993296
4.137779
-1.04562
1.088139
2.309287
-4.16739
2.775129
-2.78799
0.696347
-2.4509
-4.19234
-2.82804
0.571011
4.111883
-0.61092
2.400827
-2.36299
-0.08823
3.467719
5.504582
4.116258
3.889391
4.890745
5.12182
-3.37975
-5.32025
y
-0.06869
-1.99135
1.777794
-0.06878
-0.13836
-4.17482
-1.10869
-2.844
-2.76394
0.462263
2.666179
2.504944
-2.34078
0.649391
0.837147
1.038864
3.851517
-2.47094
-0.70171
-1.14456
-4.11826
-0.72132
3.962697
2.062056
2.348493
0.464091
2.961751
4.618828
2.698816
4.090862
4.916786
3.499403
3.43351
5.456617
z
0.047698
0.410578
-0.59179
-0.09497
-0.04686
0.710544
0.49595
0.360297
0.839965
-0.26043
-0.57073
-1.01985
0.965257
-0.06044
-0.50316
-0.11218
-1.32531
0.113473
-0.04163
-0.03058
1.04244
0.390999
-1.00523
-1.03601
-0.2791
1.858147
-1.55165
-2.54044
-2.75693
-0.85958
-1.33601
-3.26737
-0.2301
-0.11516
29
Charge Density
0.764281
-0.61047
-0.59939
-0.59943
-0.60911
-0.11273
0.264128
0.279489
0.266474
-0.11183
0.278268
0.279295
0.031091
-0.1109
0.277694
0.278495
-0.11495
0.027825
-0.11086
0.27532
-0.112
-0.11084
-0.1105
0.025272
0.02403
-0.52087
-0.21336
-0.01574
0.396825
0.482106
-0.44662
-0.15449
-0.21195
-0.01588
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
F
F
F
F
F
F
F
F
H
S
O
O
O
H
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
-3.94263
-3.83564
-4.78909
-4.89977
-3.51007
-5.52655
-3.9329
-4.14624
-5.14165
-4.92262
3.301969
5.157395
4.26963
3.301114
4.203905
5.192952
-1.38535
4.999193
-5.00491
1.351878
-5.05412
1.212596
4.949807
-1.23787
-6.07169
6.286981
5.892897
-6.30878
3.739771
3.294026
-3.31453
-3.53367
-3.77028
-3.34311
2.375095
4.294962
-5.2071
-5.95358
-4.82803
-6.57997
-7.00298
4.153273
3.836455
4.086802
5.088168
4.83194
-3.51528
-5.46532
-4.17438
-3.87402
-4.83323
-5.14018
-3.28124
-5.05041
-3.91796
-3.57886
-4.44612
-4.78801
-5.03812
1.055418
1.330025
4.616711
-1.35078
-4.92639
-1.29595
4.837998
6.232993
5.282847
-5.73626
-6.21294
1.611946
4.372251
3.7202
3.22525
-3.25672
-3.84895
-2.98821
-3.6649
-5.61604
-5.28274
-5.84423
-3.97281
-6.34588
-4.6331
0.975264
-1.37316
-1.34417
1.046335
0.092515
0.039002
1.245247
-1.09046
-1.13077
1.246331
1.549893
2.690434
0.781671
2.911631
3.499024
1.331703
0.710145
-0.52659
-0.07189
-1.71123
-0.01099
1.359064
0.754081
-1.07467
-0.03056
-2.88893
3.094475
-0.02201
-3.44297
0.304973
-2.55178
2.092578
-2.21576
2.403394
3.678491
-0.53154
2.176506
-2.71357
-3.614
-3.2464
-2.30481
4.564413
30
0.483495
0.395776
-0.15432
-0.44603
-0.21401
-0.0156
0.396921
0.481707
-0.44623
-0.15412
-0.20715
-0.01567
0.480448
0.397071
-0.15416
-0.44701
0.143295
0.144284
0.143795
0.143415
0.143513
0.144252
0.143702
0.142406
0.154581
0.154402
0.154737
0.154578
-0.29499
-0.28467
-0.29707
-0.28291
-0.2826
-0.29697
-0.29569
-0.28435
0.143614
1.754509
-0.85689
-0.85745
-0.86415
0.143779
S 77
6.461732 -5.59789 0.28235
1.755155
O 78
5.673866 -6.44644 -0.74319
-0.85681
O 79
7.269713 -4.44326 -0.35563
-0.85711
O 80
7.284613 -6.44721 1.282285
-0.86398
H 81
-0.36143 -0.26608 2.437911
0.416651
H 82
0.78102 0.767406 2.167993
0.415705
H 83
-5.10226 5.557622 -2.26837
0.143712
S 84
-5.61379 5.336624 2.659344
1.754453
O 85
-6.64258 6.431996 2.284857
-0.86412
O 86
-4.42435 5.868866 3.492802
-0.85688
O 87
-6.26021 4.05961 3.245687
-0.85762
H 88
5.585562 3.242378 -4.21154
0.143581
S 89
5.414931 6.39984 -0.39168
1.754743
O 90
5.894361 5.871022 0.980528
-0.85747
O 91
4.161833 7.302909 -0.30652
-0.85685
O 92
6.552709 7.00432 -1.25113
-0.86408
SCF Done: E(UCAM-B3LYP) = -3866.66979034 A.U. after 2 cycles
1
2
3
A
A
A
Frequencies --
5.7505
9.3726
10.5932
Red. masses --
13.7925
14.9623
16.9081
Zero-point correction = 0.573288 (Hartree/Particle)
Thermal correction to Energy = 0.635606
Thermal correction to Enthalpy = 0.636550
Thermal correction to Gibbs Free Energy = 0.467683
Sum of electronic and zero-point Energies = -3866.096502
Sum of electronic and thermal Energies = -3866.034185
Sum of electronic and thermal Enthalpies = -3866.033241
Sum of electronic and thermal Free Energies = -3866.202107
Item Value Threshold Converged?
Maximum Force
0.000018
0.000450
YES
RMS Force
0.000002
0.000300
YES
31
Table S7. DFT calculated Cartesian coordinates and charge densities for [CoIII(OH2)(FPS)]3− f.
Co
N
N
N
N
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
Atom
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
x
-0.00962
1.400811
-1.37381
1.335463
-1.31463
3.450256
-1.17019
2.763012
1.235845
-3.28619
-1.28825
-2.65706
0.021965
2.337262
-2.61634
1.099717
-3.36147
3.399555
3.328743
2.702844
2.508124
-2.40418
-2.53137
-3.24783
-0.14182
-0.32843
-4.6412
-7.25557
-4.91294
-5.74021
-7.03331
-6.19103
-0.21789
y
0.119912
1.47113
-1.23456
-1.28756
1.530067
2.528182
2.873128
1.273283
2.826653
2.650669
-2.57332
-1.04435
3.49955
-3.31872
1.38279
-2.61536
-2.29436
0.041992
-2.41933
-1.15117
3.484357
3.564825
-3.23002
0.181347
-3.23331
0.087482
0.223193
0.331529
0.625943
-0.1165
-0.07084
0.687721
-4.67778
z
-0.324
-0.2567
-0.67622
-0.20473
-0.69123
-0.20987
-0.41903
-0.29388
-0.09841
-1.11051
-0.37806
-1.1321
-0.09343
0.231854
-1.10647
0.056788
-1.17331
-0.30591
0.045937
-0.19291
-0.05183
-0.64946
-0.66465
-1.39318
0.036485
1.537113
-1.91278
-2.92632
-3.21916
-1.13258
-1.62057
-3.74358
0.384693
Charge Density
0.760827
-0.61049
-0.59848
-0.60045
-0.60918
-0.11214
0.26253
0.279211
0.267721
-0.11174
0.27805
0.279482
0.032087
-0.11078
0.278004
0.278234
-0.11494
0.02807
-0.11063
0.274393
-0.11184
-0.11109
-0.11065
0.025625
0.024972
-0.52073
-0.21179
-0.01601
0.396449
0.481559
-0.44655
-0.15449
-0.21076
32
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
F
F
F
F
F
F
F
F
H
S
O
O
O
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
-0.32646
-0.08391
-0.40257
-0.46276
-0.1362
4.885445
7.686946
5.684756
5.553072
6.932948
7.066713
0.024779
0.056165
-0.17771
0.249985
0.266115
-0.16871
4.520872
-4.31522
2.427024
-4.37344
4.39428
2.651429
-2.56399
-2.7297
-0.36402
-8.27899
0.073708
8.766227
-3.87581
-5.51944
-0.53044
0.104589
4.817288
5.073183
0.455489
-0.39284
7.631958
7.77476
7.321893
7.299776
9.281244
-7.39843
-5.10826
-5.67167
-7.01875
-6.44568
-0.00553
-0.11466
0.381482
-0.45689
-0.51387
0.339432
4.961169
7.714426
5.91243
5.451321
6.805397
7.274556
2.653441
2.80533
-4.37453
-2.42619
-2.58486
4.549311
4.620187
-4.27964
-8.43913
0.358501
8.769433
-0.16958
0.969782
-0.50116
-5.29063
-4.18121
-0.8457
0.81632
4.56651
5.473602
0.653918
-1.11549
-0.16591
-2.57579
-0.99576
1.061194
1.699735
-0.57425
-0.26751
2.04728
-0.35575
-0.46836
0.718188
-1.48865
-1.55843
0.688068
0.182087
0.720454
-0.81602
1.463398
1.743014
-0.57732
-0.25653
-1.39686
0.436809
-1.52349
0.091516
0.048998
-0.49184
-0.51362
1.361424
-3.28199
0.96792
-0.54992
-3.99384
0.129661
-1.85242
2.645409
-2.5357
1.827971
2.445257
-2.06331
1.556493
-3.07389
-4.20782
-3.25986
-2.73516
-0.0156
0.482315
0.395512
-0.15418
-0.44567
-0.2126
-0.01592
0.396325
0.481968
-0.44614
-0.15403
-0.21045
-0.01566
0.395722
0.482901
-0.4458
-0.15402
0.143316
0.1439
0.143847
0.143373
0.143938
0.144329
0.143518
0.142561
0.154688
0.154551
0.154797
0.15462
-0.29533
-0.28459
-0.29726
-0.283
-0.28294
-0.29668
-0.28297
-0.29661
0.143834
1.754426
-0.8574
-0.85702
-0.8641
33
H 76
0.420157 0.452716 2.037131
H 77
-1.11255 0.610564 1.772694
H 78
-0.60886 -7.74318 -1.05899
S 79
0.051991 -6.97464 3.794521
O 80
-0.08981 -8.51549 3.732463
O 81
-1.09523 -6.28181 4.566306
O 82
1.462269 -6.50407 4.221678
H 83
-0.33217 7.96374 -1.39639
S 84
0.558233 7.410819 3.450394
O 85
-0.58474 6.811373 4.302853
O 86
0.484337 8.951872 3.315994
O 87
1.962848 6.894478 3.841555
H 88
-6.33587 1.006487 -4.76826
S 89
-8.45501 -0.54121 -0.56041
O 90
-8.42067 0.432589 0.640387
O 91
-8.20835 -2.01781 -0.17076
O 92
-9.68617 -0.34321 -1.47868
SCF Done: E(UCAM-B3LYP) = -3866.66950009
1
2
3
A
A
A
0.416846
0.41546
0.143652
1.754623
-0.86416
-0.85725
-0.85691
0.143852
1.754685
-0.85712
-0.86395
-0.85691
0.143447
1.755238
-0.85731
-0.85708
-0.86407
A.U. after 1 cycles
Frequencies --
5.9428
8.0464
10.4516
Red. masses --
13.7164
15.2885
15.5253
Zero-point correction = 0.573086 (Hartree/Particle)
Thermal correction to Energy = 0.635452
Thermal correction to Enthalpy = 0.636396
Thermal correction to Gibbs Free Energy = 0.467099
Sum of electronic and zero-point Energies = -3866.096414
Sum of electronic and thermal Energies = -3866.034048
Sum of electronic and thermal Enthalpies = -3866.033104
Sum of electronic and thermal Free Energies = -3866.202401
Item Value Threshold Converged ?
Maximum Force
0.000003
0.000450
YES
RMS Force
0.000000
0.000300
YES
34
Table S8. DFT calculated Cartesian coordinates and charge densities for high-spin [CoIV(O•)(FPS)]3−.
Co
Atom
1
x
0.028499
y
0.238697
z
-0.12016
Charge Density
0.822258
Spin Density
1.475436
N
2
1.958836
0.748303
-0.3366
-0.6132
0.067354
N
3
-1.81003
-0.32538
-0.70639
-0.61319
0.061662
N
4
0.547554
-1.63097
-0.04501
-0.5918
0.003924
N
5
-0.46292
2.097642
-0.41394
-0.58946
0.003628
C
6
4.259454
0.669629
-0.60431
-0.09215
-0.06323
C
7
0.353593
3.194665
-0.16072
0.28625
-0.07211
C
8
3.046654
-0.10529
-0.42763
0.292899
-0.08233
C
9
2.469117
1.991315
-0.3305
0.303887
-0.16925
C
10
-1.70499
4.034078
-0.46536
-0.10436
0.04014
C
11
-2.33907
-1.5584
-0.61625
0.306303
-0.16436
C
12
-2.84276
0.497725
-1.12814
0.293331
-0.07647
C
13
1.721906
3.181673
-0.14126
0.040989
0.016558
C
14
0.442779
-3.88724
0.467364
-0.08454
-0.08057
C
15
-1.69095
2.599131
-0.65578
0.306015
-0.17239
C
16
-0.32051
-2.69753
0.148927
0.287224
-0.06706
C
17
-4.01405
-0.30529
-1.42417
-0.09603
-0.06116
C
18
3.003211
-1.45649
-0.21595
0.036551
0.027225
C
19
1.741852
-3.55142
0.381587
-0.10465
0.044306
C
20
1.792415
-2.1455
0.0441
0.306794
-0.17634
C
21
3.905847
1.964369
-0.5174
-0.1054
0.035922
C
22
-0.45437
4.397101
-0.13206
-0.08995
-0.07538
C
23
-3.71477
-1.56789
-1.07288
-0.09974
0.036511
C
24
-2.82514
1.8655
-1.08693
0.036956
0.018788
C
25
-1.66496
-2.69783
-0.11142
0.03406
0.00921
O
26
-0.17677
0.355154
1.59403
-0.33782
1.422491
C
27
-4.03882
2.629115
-1.47733
-0.20689
-0.0017
C
28
-6.30646
4.089709
-2.24717
-0.01449
0.000003
C
29
-4.04234
3.456089
-2.60081
0.397302
-0.00048
C
30
-5.22362
2.5721
-0.75089
0.48172
0.000822
C
31
-6.34858
3.28518
-1.12197
-0.44427
-7.2E-05
C
32
-5.14466
4.185789
-3.00249
-0.15106
-0.00045
35
C
33
-2.43874
-3.94966
0.100318
-0.20847
0.000065
C
34
-3.87671
-6.32224
0.502124
-0.01347
-0.00146
C
35
-2.69639
-4.43688
1.377135
0.484336
-0.00019
C
36
-2.93186
-4.70476
-0.96229
0.396912
-0.00193
C
37
-3.64502
-5.87613
-0.79273
-0.15155
0.00039
C
38
-3.40352
-5.60621
1.587884
-0.44452
0.00079
C
39
4.265091
-2.24082
-0.23042
-0.20894
-0.00237
C
40
6.632097
-3.74478
-0.26693
-0.01432
0.000434
C
41
5.260455
-2.07574
0.732223
0.397082
0.001089
C
42
4.508688
-3.1966
-1.21163
0.482652
-0.00024
C
43
5.669446
-3.94481
-1.24184
-0.44302
-0.00064
C
44
6.436492
-2.8034
0.734688
-0.1514
-0.0003
C
45
2.473266
4.453889
0.012961
-0.20593
-0.00096
C
46
3.947915
6.822382
0.300692
-0.01419
0.000105
C
47
2.444572
5.464338
-0.94803
0.396114
0.000558
C
48
3.279602
4.682361
1.123771
0.482227
-0.00087
C
49
4.012008
5.843621
1.277938
-0.4428
-0.00045
C
50
3.159403
6.641812
-0.82762
-0.15135
-7.5E-05
H
51
5.245162
0.256115
-0.7524
0.161222
0.003206
H
52
-2.57505
4.663329
-0.56959
0.15911
-0.00111
H
53
0.018624
-4.85885
0.668562
0.161578
0.00325
H
54
-4.94657
0.073162
-1.81331
0.161226
0.003103
H
55
2.603171
-4.18539
0.52302
0.15944
-0.00127
H
56
4.540002
2.83465
-0.58717
0.158505
-0.00036
H
57
-0.08408
5.386664
0.086432
0.162311
0.003077
H
58
-4.35481
-2.43498
-1.11138
0.155244
-0.00044
H
59
-4.42706
-7.2351
0.698134
0.157032
0.000057
H
60
-7.20361
4.636284
-2.51372
0.157259
-6E-06
H
61
4.532429
7.723355
0.446393
0.157289
-8E-06
H
62
7.53308
-4.34533
-0.31355
0.157004
-2.2E-05
F
63
-2.90973
3.539136
-3.31113
-0.29524
-0.00098
F
64
-5.25911
1.795975
0.337147
-0.28221
0.000002
F
65
-2.69967
-4.25345
-2.20255
-0.29699
-0.00088
36
F
66
-2.23093
-3.74196
2.419995
-0.28131
0.000094
F
67
3.567933
-3.38399
-2.14379
-0.28314
-0.00097
F
68
5.057689
-1.16719
1.694194
-0.29396
0.000001
F
69
3.336395
3.726169
2.057088
-0.28189
-0.00104
F
70
1.687616
5.274501
-2.03612
-0.29495
-4.3E-05
H
71
7.171563
-2.63037
1.510672
0.147027
-2.5E-05
S
72
5.945599
-5.20108
-2.55187
1.756894
0.000038
O
73
5.922077
-4.42109
-3.88694
-0.85588
0.000032
O
74
4.78539
-6.21221
-2.40115
-0.85573
-6.1E-05
O
75
7.333431
-5.79528
-2.20818
-0.86247
-3.7E-05
H
76
-4.00085
-6.41893
-1.65942
0.146856
-1.7E-05
S
77
-3.72134
-6.22128
3.288515
1.756849
-1.9E-05
O
78
-4.50609
-7.53693
3.064526
-0.86306
0.000007
O
79
-4.55376
-5.1171
3.980705
-0.85549
-3.5E-05
O
80
-2.32504
-6.43595
3.917576
-0.85601
0.000028
H
81
3.096067
7.388776
-1.60898
0.146841
-4.9E-05
S
82
5.069961
6.101404
2.756227
1.757239
0.000024
O
83
4.105851
6.073528
3.964945
-0.85536
0.000033
O
84
5.715806
7.487253
2.512192
-0.86245
-4.7E-05
O
85
6.085765
4.935624
2.742464
-0.85569
-5.9E-05
H
86
-5.08455
4.807173
-3.88717
0.146921
0.000033
S
87
-7.89935
3.166246
-0.14634
1.757283
-9E-06
O
88
-7.5332
3.644046
1.277856
-0.8557
-7.3E-05
O
89
-8.31375
1.677957
-0.21705
-0.85568
0.000013
O
90
-8.875
4.114996
-0.88466
-0.86282
-1.9E-05
SCF Done: E(UCAM-B3LYP) = -3865.35108108
A.U. after 1 cycles
Annihilation of the first spin contaminant:
S**2 before annihilation
3.0231, after
2.1457
1
2
3
A
A
A
Frequencies --
5.2048
10.5360
12.6182
Red. masses --
13.5001
16.0518
16.2415
Zero-point correction = 0.546767 (Hartree/Particle)
Thermal correction to Energy = 0.608527
37
Thermal correction to Enthalpy = 0.609471
Thermal correction to Gibbs Free Energy = 0.441307
Sum of electronic and zero-point Energies = -3864.804314
Sum of electronic and thermal Energies = -3864.742554
Sum of electronic and thermal Enthalpies = -3864.741610
Sum of electronic and thermal Free Energies = -3864.909775
Item Value Threshold Converged?
Maximum Force
0.000004
0.000450
YES
RMS Force
0.000001
0.000300
YES
Table S9. DFT calculated Cartesian coordinates and charge densities for high-spin [CoIV(O•)(TPPS)]3−.
Atom
Co 1
x
0.024332
y
0.042568
z
0.086957
Charge Density
0.797176
Spin Density
-0.04925
N
2
0.032541
-1.90378
-0.02472
-0.57721
-0.00804
N
3
0.00919
1.989697
-0.09018
-0.5798
0.019813
N
4
-1.91804
0.028842
-0.0282
-0.57191
0.016718
N
5
1.98363
0.04088
-0.04125
-0.57025
0.034513
C
6
-0.51591
-4.07109
-0.56927
-0.09582
0.082244
C
7
2.803335
-0.98205
0.396318
0.28027
0.041877
C
8
-0.99573
-2.72816
-0.44363
0.275764
0.043007
C
9
1.095279
-2.71786
0.191948
0.287638
0.158883
C
10
4.152468
0.780266
0.092477
-0.11406
-0.03282
C
11
-1.0459
2.814378
0.138454
0.29975
0.117744
C
12
1.05901
2.812885
-0.45539
0.280847
0.005458
C
13
2.405853
-2.3031
0.546412
-0.00505
0.018269
C
14
-4.10676
0.6312
0.357922
-0.09024
0.105586
C
15
2.798435
1.105908
-0.2365
0.288796
0.12834
C
16
-2.74181
1.067731
0.348666
0.285055
0.002244
C
17
0.604588
4.170083
-0.52836
-0.09743
0.079068
C
18
-2.32011
-2.33653
-0.60343
-0.0028
0.019858
C
19
-4.10679
-0.66161
-0.05543
-0.1124
-0.07097
C
20
-2.73862
-1.02325
-0.27616
0.286128
0.157602
C
21
0.769776
-4.0721
-0.13098
-0.11344
-0.04779
38
C
22
4.146867
-0.50446
0.532263
-0.095
0.066711
C
23
-0.6808
4.178198
-0.09486
-0.11488
-0.05281
C
24
2.384639
2.419512
-0.57689
-0.00859
0.066405
C
25
-2.35244
2.392119
0.4869
-0.02017
0.070164
O
26
0.02001
0.091159
1.819697
-0.36261
1.026541
C
27
3.431163
3.388705
-0.97595
-0.03301
-0.00344
C
28
5.404758
5.170536
-1.78802
-0.31727
0.000847
C
29
4.227771
3.10741
-2.09526
-0.09592
-0.00414
C
30
3.654943
4.574428
-0.26271
-0.10116
-0.00315
C
31
4.645097
5.459126
-0.66754
-0.0414
0.002294
C
32
5.203178
4.004049
-2.50624
-0.03806
0.00129
C
33
-3.36058
3.390167
0.923483
-0.03565
-0.00283
C
34
-5.26083
5.222545
1.789299
-0.31708
0.001646
C
35
-3.89034
3.303916
2.216842
-0.09295
-0.00757
C
36
-3.80617
4.406376
0.068364
-0.10052
0.002163
C
37
-4.75985
5.316652
0.501927
-0.03913
0.004547
C
38
-4.83336
4.227195
2.649966
-0.04093
0.0041
C
39
-3.34664
-3.30689
-1.04357
-0.02916
-0.00041
C
40
-5.2726
-5.10452
-1.93251
-0.31724
-0.00063
C
41
-3.56357
-4.51204
-0.36061
-0.1022
-5.5E-05
C
42
-4.12463
-3.01646
-2.17423
-0.09806
-0.00034
C
43
-5.07612
-3.92031
-2.62292
-0.03927
0.000152
C
44
-4.53027
-5.40414
-0.80321
-0.04009
0.000041
C
45
3.364593
-3.34423
0.973519
-0.02737
-0.00816
C
46
5.123786
-5.32815
1.809826
-0.31731
0.001591
C
47
4.577601
-3.54982
0.300055
-0.10336
0.00321
C
48
3.048291
-4.16083
2.069667
-0.09767
0.005134
C
49
3.933712
-5.14093
2.492946
-0.03932
-3.7E-05
C
50
5.4503
-4.54515
0.715937
-0.04015
-0.00091
S
51
-6.60419
-6.27244
-2.48777
1.724445
-0.00025
S
52
6.767256
6.326101
-2.29106
1.724578
-7.3E-05
S
53
6.259896
-6.70607
2.314974
1.724369
0.000091
O
54
7.651944
-6.18485
1.888258
-0.86828
-7.6E-05
39
O
55
6.023011
-6.81476
3.839133
-0.86846
-0.00239
O
56
-6.64636
-6.04943
-4.01761
-0.86862
0.000349
O
57
-6.07407
-7.64972
-2.02596
-0.86819
0.000996
O
58
6.838136
6.134188
-3.8241
-0.86798
0.001956
O
59
6.25125
7.702855
-1.81166
-0.86914
0.000578
O
60
7.994112
5.794022
-1.51913
-0.85922
0.00089
O
61
5.745542
-7.91022
1.496322
-0.85898
-0.00022
O
62
-7.85549
-5.77731
-1.73088
-0.85886
0.000083
H
63
-1.09347
-4.90396
-0.93716
0.15719
-2.6E-05
H
64
4.983961
1.465242
0.035289
0.152281
0.000051
H
65
-4.95102
1.256006
0.605794
0.155533
-0.00206
H
66
1.206113
5.00919
-0.83883
0.156979
0.000348
H
67
-4.94904
-1.32258
-0.18748
0.15214
0.001322
H
68
1.455726
-4.90264
-0.07224
0.152696
0.00178
H
69
4.977482
-1.08322
0.903461
0.156654
0.000675
H
70
-1.33345
5.026289
0.033772
0.15127
0.000948
H
71
4.058008
2.191366
-2.6532
0.135392
-0.00021
H
72
3.067243
4.783728
0.62527
0.136733
0.000044
H
73
4.834245
6.390226
-0.14366
0.140363
-0.00005
H
74
5.804667
3.835135
-3.3932
0.139128
0.000064
H
75
-3.54085
2.521355
2.883491
0.135667
-5E-06
H
76
-3.4197
4.464333
-0.94461
0.13615
0.000106
H
77
-5.2342
4.210755
3.658004
0.139774
-4.3E-05
H
78
-2.98854
-4.73085
0.533291
0.136983
-1E-06
H
79
-3.95734
-2.088
-2.71189
0.135668
0.000047
H
80
-5.6615
-3.74378
-3.51911
0.139851
0.000053
H
81
-4.71342
-6.3494
-0.30313
0.139849
0.00005
H
82
4.815416
-2.94625
-0.56982
0.136462
0.000038
H
83
2.114606
-4.0008
2.600116
0.136607
0.000021
H
84
3.736284
-5.75898
3.362444
0.139857
-3.6E-05
H
85
6.399165
-4.72349
0.220942
0.139802
0.00008
H
86
-5.11681
6.122402
-0.13094
0.13893
0.000069
S
87
-6.58228
6.404236
2.338396
1.724087
0.000001
40
O
88
-6.26581
7.681946
1.525746
-0.86835
0.000007
O
89
-6.35051
6.506469
3.863984
-0.86933
-1.1E-05
O
90
-7.8926
5.694572
1.933176
-0.85954
-2E-06
SCF Done: E(UCAM-B3LYP) = -3071.25900448
A.U. after 1 cycles
Annihilation of the first spin contaminant:
S**2 before annihilation
2.1446, after
2.0112
1
2
3
A
A
A
Frequencies --
6.3417
15.6533
16.0660
Red. masses --
13.8718
13.4130
10.6417
Zero-point correction = 0.611949 (Hartree/Particle)
Thermal correction to Energy = 0.666503
Thermal correction to Enthalpy = 0.667447
Thermal correction to Gibbs Free Energy = 0.513271
Sum of electronic and zero-point Energies = -3070.647055
Sum of electronic and thermal Energies = -3070.592502
Sum of electronic and thermal Enthalpies = -3070.591557
Item Value Threshold Converged?
Maximum Force
0.000032
0.000450
YES
RMS Force
0.000004
0.000300
YES
References
1. K. Sakai, Y. Kizaki, T. Tsubomura, K. Matsumoto, J. Mol. Catal., 1993, 79, 141-152.
2. C. J. P. Monteiro, M. M. Pereira, S. M. A. Pinto, A. V. C. Simões, G. F. F. Sá, L. G. Arnaut, S. J.
Formosinho, S.Simões, M. F. Wyatt, Tetrahedron. 2008, 64, 5132-5138.
3. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V.
Barone, B. Mennucci, G. A. Petersson, et al., Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford
CT, 2009.
41