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Radical cation and dication of a 4H-dithieno[2,3-b:3',2'-e][1,4]thiazine
Arno Schneeweis,a Andreas Neidlinger,b Guido J. Reiss,c Walter Frank,c Katja Heinze,b and
Thomas J. J. Müller*,a
aInstitut für Organische Chemie und Makromolekulare Chemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
bInstitut für Anorganische Chemie und Analytische Chemie, Johannes-Gutenberg-Universität Mainz, Duesbergweg 10-14, D-55128 Mainz, Germany
cInstitut für Anorganische Chemie und Strukturchemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
Email: [email protected]
Table of contents 1 General Considerations ................................................................................................................ 2
2 Preparation of starting materials ................................................................................................... 4
2.1 Bis(phenylsulfonyl)sulfide .............................................................................................................. 4
2.2 3,3’-Dibromo-2,2’-dithienylsulfide (3) ............................................................................................ 4
3 1H, 13C and HSQC NMR spectra of 4-(4-(tert-butyl)phenyl)-4H-dithieno[2,3-b:3',2'-e][1,4]thiazine (5) .................................................................................................................................................. 6
4 1H NMR of 52+ ∙ 2 [SbCl6]- ............................................................................................................. 9
5 Crystal Structure determination of 5 ............................................................................................ 10
6 UV/Vis spectra of 5+ and 52+ ....................................................................................................... 12
7 Computed xyz-coordinates and computed UV/Vis spectra of TD-DFT calculated structures .... 14
7.1 XYZ-coordinates for of the S0 state of the intra conformer of 5 (RB3LYP/6-311G(d)) ............... 14
7.2 XYZ-coordinates for of the S0 state of the intra conformer of 5 (RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM) ................................................................................................................ 15
7.3 XYZ-coordinates for of the S0 state of the extra conformer of 5 (RB3LYP/6-311G(d)) .............. 17
7.4 XYZ-coordinates for of the S0 state of the extra conformer of 5 (RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM) ................................................................................................................ 18
7.5 XYZ-coordinates for of the S0 state of the extra conformer of 5 and TD DFT calculation (RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM) ............................................................................. 20
7.6 XYZ-coordinates for of the D0 state of 5+ and TD DFT calculation (UB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM) ................................................................................................................ 23
7.7 XYZ-coordinates for of the S0 state of 52+ (UB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM) .......... 29
7.8 XYZ-coordinates for of the T0 state of 52+ (UB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM) .......... 40
Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2017
2
1 General Considerations
All reactions were conducted in heat gun-dried glassware under an argon atmosphere.
Solvents for reactions were directly used from a MB-SPS 800 solvent drying system (Firma
MBraun) or dried according to literature. Commercially available reagents and catalysts were
purchased and employed without further purification.
All reactions were monitored by TLC (silica gel 60, F254, Merck KGaA). The spots were
detected with UV light at λmax,exc = 254 nm and treated with iodine vapour. The crude mixtures
were absorbed on Celite® 545 (0.02-0.10 mm, Carl Roth GmbH Co.KG) prior to
chromatographic purification. Preparative flash column chromatography was conducted with
silica gel (0.04 to 0.063 mm, Macherey-Nagel) and a pressure of 1.0 bar (nitrogen) was
employed. 1H, 13C and 135-DEPT NMR spectra were recorded on Bruker Avance III 600, Bruker Avance
DRX 500, or Bruker Avance III 300 in acetone-d6 (1H δ 2.05, 13C δ 29.8) and in CDCl3 (
1H δ
7.26, 13C δ 77.0). As an internal standard for the 1H NMR the signal of the remaining protons
of the deuterated solvent was used. As internal standard for the 13C NMR the signal of CDCl3
(δ 77.0) or acetone-d6 (δ 29.8) was used. The conventional abbreviations were used as
follows: s (singlet), d (doublet), t (triplet), q (quartet), dd (doublet of doublets), m (multiplet).
The EI mass spectra were recorded on a Finnigan MAT 8200 apparatus and ESI mass
spectra on a Finnigan TSQ 7000 apparatus.
IR spectra were recorded on a Shimadzu IRAffinity-1 apparatus (ATR). The intensities of
the absorption bands are indicated by s (strong), m (medium), and w (weak).
UV/VIS spectra were recorded with a Hewlett-Packard HP8452 diode array.
Melting points were measured by using a Büchi B545 apparatus.
Elemental analyses were carried out with Elementar vario MICRO cube at the Institut für
Pharmazeutische und Medizinische Chemie at the HHU Düsseldorf.
Cyclic voltammetry experiments (EG & G potentiostatic instrumentation) were performed
under argon in dry and degassed CH2Cl2 at room temperature and at scan rates of 100, 250,
500 and 1000 mVs-1. The electrolyte was nBu4NPF6 (0.1 M). The working electrode was a
1 mm platinum disk, the counter electrode was a platinum wire, and the reference electrode
was an Ag/AgCl electrode. The potentials were corrected to the internal standard of
decamethylferrocene in CH2Cl2 (E00/+1 = -95 mV vs. ferrocene E0
0/+1 = 450 mV).1
Spectroelectrochemistry measurements were done with a quartz cuvette of the company
GAMEC Analysentechnik (thickness: 1 mm). The cell was equipped with a platinum net
working electrode, a platinum counter electrode and an Ag/AgNO3 reference electrode. As
electrolyte 0.1 M solution of [nBu4N][B(C6F5)4] in CH2Cl2 was used. All potentials are stated
1 P. Zanello, Ferrocenes, eds. A. Togni, T. Hayashi, VCH, Weinheim, 1995, 317-430.
3
versus the oxidation potential of ferrocene. The potentiostat/galvanostat was a BioLogic SP-
50 apparatus. The UV-Vis-NIR spectra were measured with a Varian Cary 5000
spectrometer.
The X-band CW-ESR spectra were measured with a Miniscope MS 300 at room
temperature. The corresponding settings were as follows: center field = 3349.03 G; sweep =
77.56 G; modulation amplitude = 100 mG; receiver gain = 0.5; microwave attenuation = 10
dB; sweep time = 120 s. As a reference Mn2+ in ZnS was used (g = 2.118, 2.066, 2.027,
1.986, 1.946, 1.906). The simulation was done with EasySpin (v. 4.5.1)2 for MatLab
(R2007b).
2 S. Stoll and A. Schweiger, J. Magn. Reson., 2006, 178, 42.
4
2 Preparation of starting materials
2.1 Bis(phenylsulfonyl)sulfide3
28 g (170 mmol) sodium benzenesulfinate were suspended in 250 mL dry diethyl ether. A
solution of 9.3 g (90 mmol) sulfur dichloride4 and 50 mL diethyl ether was added dropwise.
After that the reaction mixture was heated to 40 °C and stirred for 3 h. Then after a short rest
without heating water was added and the colourless solid was filtered of. The solid was
washed several times with water and recrystallized from acetone to give colourless crystals
(20 g, 65 mmol, 72%).
Mp 133 °C. 1H-NMR (300 MHz, CDCl3): δ 7.63 – 7.53 (m, 4 H), 7.74 – 7.66 (m, 2 H), 8.07 –
7.96 (m, 4 H). 13C-NMR (75 MHz, CDCl3): δ 128.2 (CH), 129.5 (CH), 135.0 (CH), 144.5
(Cquart). EI-MS (m/z (%)): 250 ([C12H10S3]+, 14), 141 ([C6H5O2S]+, 78), 125 ([C6H5OS]+, 16),
109 ([C6H5S]+, 9), 77 ([C6H5]+, 100).
2.2 3,3’-Dibromo-2,2’-dithienylsulfide (3)5
90 mL dry toluene and 9.0 mL (64 mmol) diisopropylamine were filled in a dry Schlenk vessel
with septum. The solution was cooled to -78 °C and then 39 mL (62 mmol) of a 1.6 M n-
butyllithium solution in n-hexane were added. The reaction mixture was stirred for 2 h at
0 °C. In the meantime a second dry Schlenk vessel was prepared by filling it with 10 g (61
mmol) 3-bromthiophene and dry toluene. The content was also cooled to 0 °C. After the time
is up the 3-bromthiophene solution is transferred to the reaction vessel and the stirring
continues for 2 h. Then the reaction mixture was cooled to -78 °C before 9.2 g (29 mmol) of
bis(phenylsulfonyl)sulfide was added. The suspension was stirred for additional 8 h at -78 °C.
The reaction was concluded by the addition of water at -78 °C. After reaching room
temperature the organic phase was extracted three times with diethyl ether. The combined
organic layers were dried with anhydrous magnesium sulfate and the solvent was removed
under vacuum. The crude product was absorbed on Celite® and purified chromatographically
3 F. Allared, J. Hellberg and T. Remonen, Tetrahedron Lett., 2002, 43, 1553. 4 Synthesized according to: G. Brauer (ed.): Handbuch der Präparativen Anorganischen Chemie, Stuttgart: Ferdinand-Enke Verlag, 3rd revised edition 1954, p. 280. 5 M. Miyasaka and A. Rajca, J. Org. Chem., 2006, 71, 3264.
5
on silica gel with n-hexane as mobile phase. On this way product 3 was obtained as a
colorless to pale yellow solid (6.9 g, 19 mmol, 66%).
Mp 53 °C. 1H-NMR (300 MHz, CDCl3): δ 7.00 (d, 3J = 5.5 Hz, 2 H), 7.34 (d, 3J = 5.5 Hz, 2 H). 13C-NMR (75 MHz, acetone-d6): δ 118.2 (Cquart), 130.3 (Cquart), 131.8 (CH), 132.1 (CH). EI-MS
(m/z (%)): 358 ([C8H481Br2S3]
+, 12), 356 ([C8H479Br81BrS3]
+, 21), 354 ([C8H479Br2S3]
+, 10), 196
([C8H4S3]+, 100), 82 ([C4H2S]+, 5).
6
3 1H, 13C and HSQC NMR spectra of 4-(4-(tert-butyl)phenyl)-4H-
dithieno[2,3-b:3',2'-e][1,4]thiazine (5)
1H NMR spectra of 5 (acetone-d6/CS2, 300 MHz, 293 K).
7
1H-NMR spectra of 5 (acetone-d6, 300 MHz, 293 K).
13C NMR spectra of 5 (acetone-d6/CS2, 75 MHz, 293 K).
10
5 Crystal Structure determination of 5
Identification code 5 (exp_1123)
Empirical formula C18 H17 N S3
Formular weight [g/mol] 343.51
Crystal description and colour needle, yellow
Crystal size 0.400 x 0.150 x 0.070
Crystal system triclinic
Space group 1
Unit cell dimiensions a = 12.112 (3) Å α = 113.51 (2)°
b = 13.064 (3) Å β = 114.37 (2)°
c = 13.586 (3) Å γ = 96.715 (18)°
Volume [Å3] 1690.6 (8)
Formula units Z 4
Calculated density [Mg/m3] 1.350
Temperature [K] 295
Measurment device type Xcalibur (Oxford Diffraction)
Radiation and wavelength [Å] Mo-Kα, λ = 0.71073
Absorption coefficient [1/mm] 0.434
F (000) 720.0
Teta range for data collection [°] 2.7933 to 28.6374
Index ranges
-15 ≤ h ≤ 15
-16 ≤ k ≤ 16
-17 ≤ l ≤ 17
Reflections collected 42642
Independent reflections 6998 [Rint = 0.107]
Observed reflections [I > 2σ(I)] 4740
Refinement method Full matrix least square on F2
Absorption correction multi scan : Tmin = 0.616, Tmax: 1.000:
Data / restraints / parameters 6998 / 0 / 407
Final R indices [I > 2σ(I)][a,b] R1 = 0.0668, wR2 = 0.1532
Goodness-of-fit on F2[c] 1.198
Largest diff. Peak and hole (max.,min.) [e.Ǻ-3] 0.54 und -0.42
Completeness [%] 99.9
[a] R1 = Σ ││F0│-│Fc││ / Σ│F0│
[b] wR2 = {Σ[w(F02-Fc
2)2] / Σ[w(F02)2]}1/2, w = 1/(σ2(F0
2)+(a·P)2+b·P) (P = [max(0,F02)+2Fc
2]1/3
[c] GooF = S = {[Σw(F02-Fc
2)2] / (m-n)}1/2, m = number of reflections, n = number of parameters
12
6 UV/Visspectraof5+and52+
UV/Vis spectrum of 5+ in dichloromethane (c = 7.4 ∙ 10-5 mol/L; T = 293 K)
UV/Vis spectrum of 5+ in acetone (T = 293 K)
14
7 Computed xyz-coordinates and computed UV/Vis spectra of TD-
DFT calculated structures
7.1 XYZ-coordinates for of the S0 state of the intra conformer of 5
(RB3LYP/6-311G(d))
C -2.833690 1.300494 0.200729
C -1.475611 1.207511 0.016217
N -0.768734 -0.000023 0.215152
C -1.475673 -1.207525 0.016249
C -2.833760 -1.300416 0.200753
S -3.839631 0.000073 0.869945
C -0.908864 -2.438602 -0.444894
C -1.841165 -3.420430 -0.604594
S -3.443010 -2.870888 -0.233595
S -3.442848 2.870975 -0.233713
C -1.840972 3.420400 -0.604754
C -0.908730 2.438522 -0.445011
C 0.664708 -0.000037 0.143693
C 1.331743 -0.000288 -1.079664
C 2.725838 -0.000289 -1.123575
C 3.494886 -0.000017 0.045852
C 2.802688 0.000246 1.266915
C 1.413598 0.000231 1.320225
C 5.033621 -0.000027 0.033503
C 5.608674 -0.000656 -1.393903
C 5.553809 1.261367 0.759507
C 5.553784 -1.260790 0.760616
H 0.145831 -2.580091 -0.637536
15
H -1.684974 -4.440241 -0.923148
H -1.684722 4.440185 -0.923362
H 0.145971 2.579924 -0.637684
H 0.758303 -0.000476 -2.001085
H 3.206412 -0.000495 -2.093882
H 3.352765 0.000454 2.201787
H 0.896067 0.000423 2.273464
H 6.700851 -0.000478 -1.350475
H 5.305927 -0.886434 -1.959019
H 5.305666 0.884469 -1.959900
H 6.647930 1.277907 0.759796
H 5.224000 1.301219 1.800010
H 5.203898 2.172046 0.265800
H 5.203918 -2.171899 0.267672
H 6.647905 -1.277313 0.760994
H 5.223903 -1.299750 1.801132
SCF Done: E(RB3LYP) = -1945.66152717 A.U. after 1 cycles
E(RB3LYP) = -5108333.6 kJ/mol
Sum of electronic and zero-point Energies= -1945.358781
Sum of electronic and thermal Energies= -1945.338439
Sum of electronic and thermal Enthalpies= -1945.337495
Sum of electronic and thermal Free Energies= -1945.409542
7.2 XYZ-coordinates for of the S0 state of the intra conformer of 5
(RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)
C -2.833690 1.300494 0.200729
C -1.475611 1.207511 0.016217
N -0.768734 -0.000023 0.215152
C -1.475673 -1.207525 0.016249
C -2.833760 -1.300416 0.200753
S -3.839631 0.000073 0.869945
C -0.908864 -2.438602 -0.444894
C -1.841165 -3.420430 -0.604594
S -3.443010 -2.870888 -0.233595
16
S -3.442848 2.870975 -0.233713
C -1.840972 3.420400 -0.604754
C -0.908730 2.438522 -0.445011
C 0.664708 -0.000037 0.143693
C 1.331743 -0.000288 -1.079664
C 2.725838 -0.000289 -1.123575
C 3.494886 -0.000017 0.045852
C 2.802688 0.000246 1.266915
C 1.413598 0.000231 1.320225
C 5.033621 -0.000027 0.033503
C 5.608674 -0.000656 -1.393903
C 5.553809 1.261367 0.759507
C 5.553784 -1.260790 0.760616
H 0.145831 -2.580091 -0.637536
H -1.684974 -4.440241 -0.923148
H -1.684722 4.440185 -0.923362
H 0.145971 2.579924 -0.637684
H 0.758303 -0.000476 -2.001085
H 3.206412 -0.000495 -2.093882
H 3.352765 0.000454 2.201787
H 0.896067 0.000423 2.273464
H 6.700851 -0.000478 -1.350475
H 5.305927 -0.886434 -1.959019
H 5.305666 0.884469 -1.959900
H 6.647930 1.277907 0.759796
H 5.224000 1.301219 1.800010
H 5.203898 2.172046 0.265800
H 5.203918 -2.171899 0.267672
H 6.647905 -1.277313 0.760994
H 5.223903 -1.299750 1.801132
SCF Done: E(RB3LYP) = -1945.46481809 A.U. after 1 cycles
E(RB3LYP) = -5107817.1 kJ/mol
Sum of electronic and zero-point Energies= -1945.161095
Sum of electronic and thermal Energies= -1945.140781
Sum of electronic and thermal Enthalpies= -1945.139837
Sum of electronic and thermal Free Energies= -1945.212116
17
7.3 XYZ-coordinates for of the S0 state of the extra conformer of 5
(RB3LYP/6-311G(d))
N -0.748068 0.006841 -0.520526
S -2.985077 -0.011834 1.588674
C -1.528196 1.192904 -0.432529
C -1.510331 -1.190936 -0.434552
C -2.556259 1.295958 0.470041
C -2.536828 -1.311060 0.467735
C -1.417333 -2.320836 -1.308351
C -1.451711 2.325953 -1.303793
C -2.400201 3.263312 -1.026663
C -2.351740 -3.272798 -1.033121
S -3.461144 2.767550 0.258712
S -3.419825 -2.795446 0.253300
C 0.654755 0.018157 -0.320966
C 1.367797 1.218704 -0.213860
C 1.385229 -1.176413 -0.214237
C 2.762352 -1.153964 -0.040039
C 2.750077 1.218410 -0.039648
C 3.493278 0.038737 0.045050
C 5.017966 0.007626 0.240018
C 5.355936 -0.717725 1.562314
C 5.626262 1.419808 0.300715
18
C 5.676417 -0.747229 -0.936891
H -0.683849 -2.407153 -2.099247
H -0.719206 2.425098 -2.094064
H -2.550145 4.223173 -1.498387
H -2.487595 -4.233689 -1.507018
H 0.848679 2.167748 -0.239546
H 0.878353 -2.132047 -0.240561
H 3.273046 -2.108327 0.040337
H 3.241304 2.180748 0.039541
H 4.989700 -1.747154 1.567703
H 6.439013 -0.751799 1.717923
H 4.907683 -0.203552 2.416781
H 5.444393 1.984610 -0.617978
H 5.232118 1.999837 1.139688
H 6.709612 1.352097 0.432473
H 5.461192 -0.253961 -1.888823
H 6.763535 -0.781897 -0.812503
H 5.320553 -1.777593 -1.010930
SCF Done: E(RB3LYP) = -1945.66075886 A.U. after 1 cycles
E(RB3LYP) = -5108331.6 kJ/mol
Sum of electronic and zero-point Energies= -1945.357583
Sum of electronic and thermal Energies= -1945.337530
Sum of electronic and thermal Enthalpies= -1945.336586
Sum of electronic and thermal Free Energies= -1945.407120
ΔEintra-extra = - 2.0 kJ/mol
7.4 XYZ-coordinates for of the S0 state of the extra conformer of 5
(RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)
N -0.750191 0.005936 -0.511806
S -3.023653 -0.010525 1.572702
C -1.528192 1.195009 -0.426845
C -1.511318 -1.194172 -0.427438
19
C -2.571046 1.298753 0.463380
C -2.552406 -1.313010 0.463108
C -1.400371 -2.331887 -1.294798
C -1.432006 2.334991 -1.292922
C -2.379605 3.279052 -1.023521
C -2.334457 -3.289366 -1.025399
S -3.460973 2.783231 0.248162
S -3.421721 -2.809539 0.247267
C 0.654695 0.017239 -0.315402
C 1.367311 1.221289 -0.201811
C 1.387342 -1.180019 -0.215809
C 2.767407 -1.156454 -0.041210
C 2.752116 1.221393 -0.027177
C 3.497777 0.039277 0.052425
C 5.024321 0.008294 0.241806
C 5.369042 -0.743138 1.549764
C 5.628779 1.422523 0.326197
C 5.677842 -0.726008 -0.953152
H -0.655742 -2.421433 -2.075779
H -0.687282 2.435820 -2.072438
H -2.517550 4.242874 -1.493245
H -2.459361 -4.254606 -1.495859
H 0.848403 2.171009 -0.231935
H 0.883262 -2.137227 -0.257313
H 3.281524 -2.110713 0.029814
H 3.244001 2.184083 0.054678
H 5.000445 -1.773292 1.535858
H 6.454766 -0.779951 1.694032
H 4.927728 -0.240885 2.417013
H 5.442800 2.000765 -0.584942
H 5.229148 1.985861 1.175818
H 6.713411 1.352408 0.457119
20
H 5.462278 -0.209779 -1.894645
H 6.765948 -0.765300 -0.828419
H 5.315703 -1.754470 -1.044377
SCF Done: E(RB3LYP) = -1945.46354748 A.U. after 1 cycles
E(RB3LYP) = -5107813.8 kJ/mol
Sum of electronic and zero-point Energies= -1945.159371
Sum of electronic and thermal Energies= -1945.139362
Sum of electronic and thermal Enthalpies= -1945.138418
Sum of electronic and thermal Free Energies= -1945.208890
ΔEintra-extra = -3.3 kJ/mol
7.5 XYZ-coordinates for of the S0 state of the extra conformer of 5 and
TD DFT calculation (RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)
N -0.75019100 0.00593600 -0.51180600
S -3.02365300 -0.01052500 1.57270200
C -1.52819200 1.19501000 -0.42684500
C -1.51131800 -1.19417200 -0.42743800
C -2.57104700 1.29875300 0.46338000
C -2.55240700 -1.31301000 0.46310800
C -1.40037100 -2.33188800 -1.29479800
C -1.43200600 2.33499100 -1.29292200
C -2.37960500 3.27905200 -1.02352100
C -2.33445700 -3.28936600 -1.02539900
S -3.46097300 2.78323100 0.24816200
21
S -3.42172200 -2.80953900 0.24726700
H -0.68728200 2.43582000 -2.07243900
H -0.65574200 -2.42143300 -2.07577900
H -2.51755000 4.24287400 -1.49324500
H -2.45936100 -4.25460600 -1.49585900
C 0.65469500 0.01723900 -0.31540200
C 1.36731100 1.22128900 -0.20181100
C 1.38734200 -1.18001900 -0.21580900
C 2.76740700 -1.15645400 -0.04121000
C 2.75211700 1.22139300 -0.02717700
C 3.49777700 0.03927700 0.05242500
H 0.88326200 -2.13722800 -0.25731300
H 0.84840400 2.17101000 -0.23193500
H 3.28152400 -2.11071300 0.02981400
H 3.24400100 2.18408300 0.05467800
C 5.02432100 0.00829400 0.24180600
C 5.36904300 -0.74313800 1.54976400
H 5.00044600 -1.77329200 1.53585800
H 6.45476700 -0.77995100 1.69403200
H 4.92772800 -0.24088500 2.41701400
C 5.62877900 1.42252300 0.32619700
H 5.44280000 2.00076500 -0.58494200
H 5.22914800 1.98586100 1.17581800
H 6.71341200 1.35240900 0.45711900
C 5.67784300 -0.72600800 -0.95315200
H 5.46227900 -0.20977900 -1.89464500
H 6.76594900 -0.76530000 -0.82841900
H 5.31570400 -1.75447000 -1.04437700
SCF Done: E(RB3LYP) = -1945.46354748 A.U. after 1 cycles
After PCM corrections, the SCF energy is -1945.46692415 a.u.
Sum of electronic and zero-point Energies= -1945.159371
Sum of electronic and thermal Energies= -1945.139362
Sum of electronic and thermal Enthalpies= -1945.138418
Sum of electronic and thermal Free Energies= -1945.208890
HOMO -5.1065 eV
LUMO -0.7195 eV
22
Relevant excitation energies and oscillator strengths:
Excited State 1: Singlet-A 3.6206 eV 342.44 nm f=0.0044
90 -> 92 0.69035
This state for optimization and/or second-order correction.
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited State 2: Singlet-A 3.7369 eV 331.78 nm f=0.1613
90 -> 91 0.67922
Excited State 3: Singlet-A 4.4105 eV 281.11 nm f=0.0177
87 -> 94 0.12205
90 -> 93 0.66906
Excited State 4: Singlet-A 4.5915 eV 270.03 nm f=0.0351
89 -> 91 0.43417
89 -> 92 0.16703
90 -> 94 0.43327
90 -> 95 -0.20503
90 -> 96 0.10786
Excited State 5: Singlet-A 4.5970 eV 269.71 nm f=0.0479
89 -> 91 0.19698
89 -> 92 -0.38571
89 -> 95 0.12574
90 -> 94 0.18552
90 -> 95 0.46069
90 -> 98 0.12050
Excited State 6: Singlet-A 4.6927 eV 264.21 nm f=0.0675
88 -> 91 -0.11350
89 -> 91 0.10913
89 -> 92 0.50804
90 -> 94 -0.10294
90 -> 95 0.42981
Excited State 7: Singlet-A 4.7013 eV 263.72 nm f=0.2274
23
88 -> 92 -0.11002
89 -> 91 0.45746
89 -> 92 -0.11172
90 -> 94 -0.45321
90 -> 95 -0.10729
Excited State 8: Singlet-A 5.0321 eV 246.39 nm f=0.1111
90 -> 94 -0.10269
90 -> 96 0.59928
90 -> 97 0.31016
7.6 XYZ-coordinates for of the D0 state of 5+ and TD DFT calculation
(UB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)
N 0.79028300 -0.00002300 0.00910700
S 4.00073800 0.00009900 -0.00749900
C 1.46598000 -1.20680100 0.00492600
C 1.46587800 1.20680000 0.00493900
C 2.86266900 -1.31014700 -0.00257900
C 2.86256100 1.31024900 -0.00251600
C 0.83096200 2.48991300 0.00780000
C 0.83115000 -2.48995900 0.00778800
C 1.73269100 -3.50898000 0.00247200
C 1.73242600 3.50900300 0.00248500
S 3.38532300 -2.96836900 -0.00613700
S 3.38510600 2.96850600 -0.00608500
H -0.24024700 -2.63118000 0.01355600
24
H -0.24044600 2.63106900 0.01351500
H 1.53035500 -4.57097700 0.00305700
H 1.53002400 4.57098600 0.00305700
C -0.66193600 -0.00010300 0.01608700
C -1.34369400 -0.00023900 1.22948500
C -1.35570900 -0.00007500 -1.19472100
C -2.74728200 -0.00013500 -1.17552800
C -2.73992600 -0.00028200 1.22634200
C -3.47259200 -0.00019800 0.03038800
H -0.81310700 -0.00004700 -2.13432500
H -0.79315800 -0.00032800 2.16449600
H -3.27272700 -0.00014000 -2.12447100
H -3.25118100 -0.00040200 2.18073100
C -5.01127600 -0.00001700 -0.00209800
C -5.50485700 1.26407900 -0.74600600
H -5.13690900 1.30379100 -1.77533700
H -6.59916600 1.27305800 -0.78351700
H -5.17568200 2.17426100 -0.23426400
C -5.62564900 -0.00098300 1.41025000
H -5.33667400 -0.88900900 1.98174600
H -5.33699700 0.88641500 1.98287600
H -6.71678800 -0.00108200 1.33109600
C -5.50540200 -1.26276700 -0.74788400
H -5.17646200 -2.17387600 -0.23764400
H -6.59971800 -1.27128600 -0.78519000
H -5.13775400 -1.30102600 -1.77737500
SCF Done: E(UB3LYP) = -1945.30043619 A.U. after 1 cycles
After PCM corrections, the SCF energy is -1945.30630762 a.u.
Sum of electronic and zero-point Energies= -1944.995593
Sum of electronic and thermal Energies= -1944.975504
Sum of electronic and thermal Enthalpies= -1944.974560
Sum of electronic and thermal Free Energies= -1945.047397
25
The percentage contributions of a transition to the excited state were calculated by using the following equation6:
% ∑
100
Relevant excitation energies and oscillator strengths: Excited State 1: ?Spin -A 2.0849 eV 594.68 nm f=0.0139 89B -> 90B 0.99629 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density. Excited State 2: ?Spin -A 2.4470 eV 506.69 nm f=0.0263 90A -> 91A 0.15322 85B -> 90B -0.10229 86B -> 90B -0.44651 88B -> 90B 0.86716 Excited State 3: ?Spin -A 2.4547 eV 505.09 nm f=0.0855 90A -> 91A -0.26684 85B -> 90B 0.14635 86B -> 90B 0.77558 87B -> 90B -0.22114 88B -> 90B 0.49204 Excited State 4: ?Spin -A 2.6299 eV 471.45 nm f=0.0096 85B -> 90B -0.11936 86B -> 90B 0.26331 87B -> 90B 0.95460 Excited State 5: ?Spin -A 2.7079 eV 457.87 nm f=0.0090 86A -> 92A -0.15293 90A -> 91A 0.93082 81B -> 91B 0.10870 85B -> 90B -0.13514 86B -> 90B 0.27407 86B -> 93B 0.19442 87B -> 90B -0.10257 Excited State 6: ?Spin -A 3.0544 eV 405.92 nm f=0.0327 90A -> 91A 0.15884 85B -> 90B 0.96523 87B -> 90B 0.14512 Excited State 7: ?Spin -A 3.4226 eV 362.25 nm f=0.0197 81A -> 92A -0.11273 86A -> 91A -0.41045 86A -> 99A 0.10332 88A -> 92A -0.21196 90A -> 92A 0.71507 81B -> 90B 0.17872
6 R. A. Vogt, T. G. Gray, C. E. Crespo‐Hernández, J. Am. Chem. Soc. 2012, 134, 14808‐14817.
26
81B -> 93B 0.14298 86B -> 91B 0.59581 89B -> 93B 0.19009 Excited State 8: ?Spin -A 3.7370 eV 331.78 nm f=0.0000 78A ->107A 0.10010 87A -> 91A 0.16670 87A -> 94A -0.11563 87A -> 95A -0.49760 89A -> 93A -0.49084 89A -> 94A 0.38309 87B -> 91B 0.16742 87B -> 94B -0.19920 87B -> 95B -0.46154 88B -> 92B 0.55313 88B -> 94B -0.28194 Excited State 9: ?Spin -A 3.8430 eV 322.62 nm f=0.0014 85A -> 92A 0.18011 86A -> 92A 0.25445 88A -> 91A 0.68854 88A -> 99A -0.11099 90A -> 91A 0.10746 85B -> 93B -0.20592 86B -> 93B -0.21328 89B -> 91B -0.63937 89B -> 99B 0.11723 Excited State 10: ?Spin -A 3.8895 eV 318.77 nm f=0.0000 90A -> 93A 0.76367 90A -> 94A 0.60554 90A -> 95A -0.13527 90A -> 98A 0.14718 Excited State 11: ?Spin -A 4.1420 eV 299.33 nm f=0.0120 85A -> 91A 0.24166 86A -> 91A 0.39744 87A -> 91A 0.15132 88A -> 92A 0.42617 90A -> 92A 0.56083 80B -> 90B 0.15864 81B -> 90B -0.14443 84B -> 90B 0.11368 85B -> 91B -0.25599 86B -> 91B -0.17005 87B -> 91B 0.11257 89B -> 93B -0.36509 Excited State 12: ?Spin -A 4.2752 eV 290.01 nm f=0.0151 85A -> 91A -0.25639 86A -> 91A 0.21609 88A -> 92A -0.20528 90A -> 92A 0.20628 80B -> 90B 0.22013 81B -> 90B 0.68930 84B -> 90B 0.20983 85B -> 91B 0.16306 86B -> 91B -0.44361 89B -> 93B 0.13644
27
Excited State 13: ?Spin -A 4.2976 eV 288.50 nm f=0.0055 90A -> 92A -0.10313 81B -> 90B -0.18630 84B -> 90B 0.95933 86B -> 91B 0.11864 Excited State 14: ?Spin -A 4.3954 eV 282.08 nm f=0.0000 90A -> 93A -0.63848 90A -> 94A 0.73255 90A -> 95A -0.16204 90A -> 98A 0.13705 Excited State 15: ?Spin -A 4.4037 eV 281.54 nm f=0.0000 90A -> 96A 0.98786 Excited State 16: ?Spin -A 4.5071 eV 275.09 nm f=0.0005 87A -> 93A -0.13584 89A -> 91A 0.73969 89A -> 95A -0.27859 83B -> 90B 0.42476 87B -> 92B -0.18151 88B -> 91B -0.23234 88B -> 94B 0.10369 88B -> 95B 0.24582 Excited State 17: ?Spin -A 4.5147 eV 274.62 nm f=0.0016 89A -> 91A -0.35846 89A -> 95A 0.12497 83B -> 90B 0.88384 88B -> 91B 0.11634 88B -> 95B -0.12371 Excited State 18: ?Spin -A 4.5731 eV 271.11 nm f=0.0011 85A -> 91A 0.20906 86A -> 91A -0.17747 87A -> 91A 0.44780 87A -> 94A -0.10986 87A -> 95A -0.25623 89A -> 93A 0.26508 89A -> 94A -0.17446 90A -> 92A -0.19190 81B -> 90B 0.42425 83B -> 90B 0.10874 85B -> 91B -0.19536 86B -> 91B 0.11073 87B -> 91B 0.27978 87B -> 94B -0.13893 87B -> 95B -0.23376 88B -> 92B -0.29344 88B -> 94B 0.10500 89B -> 93B -0.12527 Excited State 19: ?Spin -A 4.6354 eV 267.47 nm f=0.0018 85A -> 91A 0.35622 86A -> 91A -0.15121 87A -> 91A -0.18347 87A -> 94A 0.14738 87A -> 95A 0.28571
28
88A -> 92A 0.19061 89A -> 93A -0.22988 89A -> 94A 0.12969 89A -> 95A -0.13137 90A -> 92A -0.18337 81B -> 90B 0.42719 85B -> 91B -0.32576 86B -> 91B 0.10541 87B -> 92B -0.11123 87B -> 94B 0.18115 87B -> 95B 0.26638 88B -> 92B 0.26746 88B -> 95B 0.14588 89B -> 93B -0.24005 Excited State 20: ?Spin -A 4.6422 eV 267.08 nm f=0.0000 78B -> 90B -0.11869 82B -> 90B 0.99008 Excited State 21: ?Spin -A 4.6513 eV 266.56 nm f=0.0101 88A -> 91A -0.11362 90A -> 94A 0.21600 90A -> 95A 0.94350 90A -> 99A 0.10500 89B -> 91B -0.15486 Excited State 22: ?Spin -A 4.7029 eV 263.63 nm f=0.0012 87A -> 93A 0.36355 87A -> 94A -0.22914 87A -> 95A 0.17304 89A -> 91A 0.53330 89A -> 94A 0.11995 89A -> 95A 0.25703 87B -> 92B 0.30677 87B -> 95B 0.16444 88B -> 91B 0.48032 88B -> 94B -0.15138 88B -> 95B -0.24937 Excited State 23: ?Spin -A 4.7574 eV 260.61 nm f=0.3633 86A -> 92A -0.24129 88A -> 91A 0.66823 88A -> 99A 0.10611 90A -> 95A 0.17954 90A -> 99A -0.21260 86B -> 93B 0.15197 89B -> 91B 0.54733
29
7.7 XYZ-coordinates for of the S0 state of 52+ (UB3LYP/6-31G(d,p),
SCRF(IEFPCM, DCM)
N 0.79476700 -0.00063900 0.00637000
S 3.95159000 0.00161500 -0.00326600
C 1.44323900 -1.20100000 -0.03019300
C 1.44184600 1.20075200 0.03640900
C 2.87380300 -1.30536600 -0.01880300
C 2.87203200 1.30714000 0.01573000
C 0.81622200 2.47854700 0.11883700
C 0.81913500 -2.47975000 -0.11168100
C 1.73576600 -3.48338100 -0.13780600
C 1.73148600 3.48368700 0.13688700
S 3.39625800 -2.95076100 -0.07938600
S 3.39245900 2.95350100 0.07019900
H -0.24834300 -2.63756100 -0.14866100
H -0.25125600 2.63506700 0.16125200
H 1.54216900 -4.54655500 -0.19421500
H 1.53660900 4.54672800 0.19145000
C -0.66289600 -0.00208800 0.01334600
C -1.33566400 -0.50179700 1.12740600
C -1.34960500 0.49807800 -1.09612600
C -2.73815300 0.48045200 -1.07659600
C -2.72856500 -0.48642800 1.12721300
C -3.46269900 -0.00324900 0.03132200
H -0.81157100 0.86529500 -1.96303300
30
H -0.78747700 -0.86912700 1.98789400
H -3.26316600 0.84793000 -1.95095000
H -3.23874000 -0.85646600 2.00708200
C -4.99834100 -0.00153600 0.00054300
C -5.50716200 1.43277200 -0.28237500
H -5.15552900 1.81600400 -1.24432300
H -6.60127400 1.43564200 -0.30673900
H -5.18372500 2.12700500 0.49962500
C -5.60917100 -0.47806100 1.33112500
H -5.32719300 -1.50889200 1.56766800
H -5.31420600 0.16348300 2.16774200
H -6.69995700 -0.44603600 1.25959600
C -5.47396200 -0.95025800 -1.12771000
H -5.13739200 -1.97601300 -0.94679000
H -6.56772400 -0.95398300 -1.16948200
H -5.10338600 -0.63880500 -2.10860400
SCF Done: E(UB3LYP) = -1945.07461541 A.U. after 1 cycles
After PCM corrections, the SCF energy is -1945.08535247 a.u.
Sum of electronic and zero-point Energies= -1944.768626 Sum of electronic and thermal Energies= -1944.748997 Sum of electronic and thermal Enthalpies= -1944.748053 Sum of electronic and thermal Free Energies= -1944.816853
HOMO -8.0464 eV
LUMO -5.8861 eV
Excitation energies and oscillator strengths:
Excited State 1: Triplet-A 1.2498 eV 992.06 nm f=0.0000
87A -> 90A 0.42719
89A -> 90A -0.63881
87B -> 90B -0.42719
89B -> 90B 0.63881
This state for optimization and/or second-order correction.
Copying the excited state density for this state as the 1-particle RhoCI density.
31
Excited State 2: Triplet-A 1.5695 eV 789.97 nm f=0.0000
86A -> 90A 0.83527
86B -> 90B -0.83527
Excited State 3: Triplet-A 1.6195 eV 765.59 nm f=0.0000
87A -> 90A 0.59357
88A -> 90A -0.21567
89A -> 90A 0.36759
87B -> 90B -0.59357
88B -> 90B 0.21567
89B -> 90B -0.36759
Excited State 4: Singlet-A 1.6531 eV 750.00 nm f=0.1041
88A -> 90A -0.11479
89A -> 90A 0.66058
88B -> 90B -0.11479
89B -> 90B 0.66058
Excited State 5: Triplet-A 1.7020 eV 728.45 nm f=0.0000
87A -> 90A 0.22169
88A -> 90A 0.67582
87B -> 90B -0.22169
88B -> 90B -0.67582
Excited State 6: Singlet-A 1.7613 eV 703.92 nm f=0.0099
88A -> 90A 0.69159
89A -> 90A 0.10030
88B -> 90B 0.69159
89B -> 90B 0.10030
Excited State 7: Singlet-A 1.9805 eV 626.02 nm f=0.0000
87A -> 90A 0.67013
32
87B -> 90B 0.67013
Excited State 8: Triplet-A 2.4630 eV 503.39 nm f=0.0000
84A -> 90A -0.71654
84B -> 90B 0.71654
Excited State 9: Singlet-A 2.6704 eV 464.28 nm f=0.0182
84A -> 90A 0.59282
86A -> 90A -0.32502
84B -> 90B 0.59282
86B -> 90B -0.32502
Excited State 10: Singlet-A 2.9072 eV 426.48 nm f=0.2363
84A -> 90A 0.33684
86A -> 90A 0.51972
87A -> 91A -0.15363
89A -> 91A 0.10192
84B -> 90B 0.33684
86B -> 90B 0.51972
87B -> 91B -0.15363
89B -> 91B 0.10192
Excited State 11: Triplet-A 3.0692 eV 403.96 nm f=0.0000
85A -> 90A 0.70215
85B -> 90B -0.70215
Excited State 12: Singlet-A 3.0796 eV 402.60 nm f=0.0043
85A -> 90A 0.70127
85B -> 90B 0.70127
Excited State 13: Triplet-A 3.3401 eV 371.19 nm f=0.0000
82A -> 90A -0.37531
33
83A -> 90A 0.58739
82B -> 90B 0.37531
83B -> 90B -0.58739
Excited State 14: Singlet-A 3.3627 eV 368.70 nm f=0.0008
82A -> 90A -0.45058
83A -> 90A 0.53633
82B -> 90B -0.45058
83B -> 90B 0.53633
Excited State 15: Triplet-A 3.3815 eV 366.66 nm f=0.0000
82A -> 90A 0.58946
83A -> 90A 0.36991
82B -> 90B -0.58946
83B -> 90B -0.36991
Excited State 16: Singlet-A 3.4054 eV 364.08 nm f=0.0000
82A -> 90A 0.53733
83A -> 90A 0.45385
82B -> 90B 0.53733
83B -> 90B 0.45385
Excited State 17: Triplet-A 3.5341 eV 350.82 nm f=0.0000
66A -> 90A 0.10273
84A -> 92A -0.16694
86A -> 91A -0.13450
86A -> 92A 0.15418
87A -> 91A 0.52759
89A -> 91A -0.42492
66B -> 90B -0.10273
84B -> 92B 0.16694
86B -> 91B 0.13450
34
86B -> 92B -0.15418
87B -> 91B -0.52759
89B -> 91B 0.42492
Excited State 18: Triplet-A 3.5390 eV 350.34 nm f=0.0000
77A -> 90A -0.29828
77A -> 92A -0.10786
80A -> 90A 0.24171
86A -> 91A -0.53274
87A -> 91A -0.13626
87A -> 92A -0.23783
89A -> 91A 0.10117
89A -> 92A 0.14178
77B -> 90B 0.29828
77B -> 92B 0.10786
80B -> 90B -0.24171
86B -> 91B 0.53274
87B -> 91B 0.13626
87B -> 92B 0.23783
89B -> 91B -0.10117
89B -> 92B -0.14178
Excited State 19: Triplet-A 3.7565 eV 330.05 nm f=0.0000
70A -> 90A -0.13235
77A -> 90A -0.43852
80A -> 90A 0.16456
84A -> 91A 0.11556
86A -> 91A 0.39738
88A -> 91A 0.13709
88A -> 96A 0.19519
89A -> 93A 0.13487
89A -> 95A -0.19851
35
70B -> 90B 0.13235
77B -> 90B 0.43852
80B -> 90B -0.16456
84B -> 91B -0.11556
86B -> 91B -0.39738
88B -> 91B -0.13709
88B -> 96B -0.19519
89B -> 93B -0.13487
89B -> 95B 0.19851
Excited State 20: Triplet-A 3.7829 eV 327.75 nm f=0.0000
77A -> 90A 0.22513
80A -> 90A -0.11611
86A -> 91A -0.18247
88A -> 91A 0.16028
88A -> 94A -0.14208
88A -> 96A 0.41806
89A -> 93A 0.29053
89A -> 94A 0.10975
89A -> 95A -0.42045
77B -> 90B -0.22513
80B -> 90B 0.11611
86B -> 91B 0.18247
88B -> 91B -0.16028
88B -> 94B 0.14208
88B -> 96B -0.41806
89B -> 93B -0.29053
89B -> 94B -0.10975
89B -> 95B 0.42045
Excited State 21: Singlet-A 3.9507 eV 313.83 nm f=0.0574
89A -> 91A 0.69247
36
89B -> 91B 0.69247
Excited State 22: Triplet-A 3.9681 eV 312.45 nm f=0.0000
87A -> 91A -0.43335
89A -> 91A -0.54507
87B -> 91B 0.43335
89B -> 91B 0.54507
Excited State 23: Triplet-A 4.1229 eV 300.72 nm f=0.0000
80A -> 90A -0.21057
84A -> 91A 0.23438
87A -> 92A -0.13757
88A -> 91A 0.57162
89A -> 93A -0.13010
89A -> 95A 0.17646
80B -> 90B 0.21057
84B -> 91B -0.23438
87B -> 92B 0.13757
88B -> 91B -0.57162
89B -> 93B 0.13010
89B -> 95B -0.17646
Excited State 24: Singlet-A 4.1734 eV 297.08 nm f=0.0109
88A -> 91A 0.69441
88B -> 91B 0.69441
Excited State 25: Triplet-A 4.2037 eV 294.94 nm f=0.0000
77A -> 90A 0.13193
78A -> 90A -0.11424
80A -> 90A 0.27820
81A -> 90A 0.59551
88A -> 91A 0.11036
37
77B -> 90B -0.13193
78B -> 90B 0.11424
80B -> 90B -0.27820
81B -> 90B -0.59551
88B -> 91B -0.11036
Excited State 26: Singlet-A 4.2133 eV 294.27 nm f=0.0032
81A -> 90A 0.69324
81B -> 90B 0.69324
Excited State 27: Triplet-A 4.2269 eV 293.32 nm f=0.0000
70A -> 90A 0.11501
76A -> 90A 0.12406
77A -> 90A 0.22937
79A -> 90A 0.13436
80A -> 90A 0.44957
81A -> 90A -0.35572
86A -> 91A 0.11086
88A -> 91A 0.19280
70B -> 90B -0.11501
76B -> 90B -0.12406
77B -> 90B -0.22937
79B -> 90B -0.13436
80B -> 90B -0.44957
81B -> 90B 0.35572
86B -> 91B -0.11086
88B -> 91B -0.19280
Excited State 28: Singlet-A 4.3143 eV 287.38 nm f=0.0361
79A -> 90A 0.23780
80A -> 90A 0.62696
79B -> 90B 0.23780
38
80B -> 90B 0.62696
Excited State 29: Triplet-A 4.3594 eV 284.41 nm f=0.0000
76A -> 90A -0.11798
77A -> 90A -0.20398
78A -> 90A -0.18819
84A -> 91A -0.49033
86A -> 91A -0.12569
87A -> 92A 0.28188
88A -> 91A 0.20775
89A -> 92A -0.11109
89A -> 95A 0.10542
76B -> 90B 0.11798
77B -> 90B 0.20398
78B -> 90B 0.18819
84B -> 91B 0.49033
86B -> 91B 0.12569
87B -> 92B -0.28188
88B -> 91B -0.20775
89B -> 92B 0.11109
89B -> 95B -0.10542
Excited State 30: Triplet-A 4.3901 eV 282.42 nm f=0.0000
76A -> 90A 0.17716
78A -> 90A 0.59336
81A -> 90A 0.12406
84A -> 91A -0.18710
87A -> 92A 0.11792
88A -> 91A 0.14095
88A -> 96A -0.11991
76B -> 90B -0.17716
78B -> 90B -0.59336
39
81B -> 90B -0.12406
84B -> 91B 0.18710
87B -> 92B -0.11792
88B -> 91B -0.14095
88B -> 96B 0.11991
Excited State 31: Singlet-A 4.4509 eV 278.56 nm f=0.0021
76A -> 90A 0.16339
78A -> 90A 0.66443
76B -> 90B 0.16339
78B -> 90B 0.66443
Excited State 32: Triplet-A 4.5266 eV 273.90 nm f=0.0000
79A -> 90A 0.66390
80A -> 90A -0.19388
79B -> 90B -0.66390
80B -> 90B 0.19388
Excited State 33: Singlet-A 4.5395 eV 273.12 nm f=0.0014
77A -> 90A 0.11282
79A -> 90A 0.65414
80A -> 90A -0.22908
77B -> 90B 0.11282
79B -> 90B 0.65414
80B -> 90B -0.22908
Excited State 34: Singlet-A 4.6020 eV 269.41 nm f=0.0151
77A -> 90A 0.59865
80A -> 90A 0.12823
84A -> 91A 0.12603
86A -> 91A -0.23623
77B -> 90B 0.59865
40
80B -> 90B 0.12823
84B -> 91B 0.12603
86B -> 91B -0.23623
Excited State 35: Singlet-A 4.6109 eV 268.89 nm f=0.6479
87A -> 91A 0.64908
87B -> 91B 0.64908
7.8 XYZ-coordinates for of the T0 state of 52+ (UB3LYP/6-31G(d,p),
SCRF(IEFPCM, DCM)
N -0.72820100 0.00008500 -0.44812300
S -3.39389200 -0.00122900 1.21182600
C -1.49872100 1.19940600 -0.43350800
C -1.49338900 -1.20325100 -0.42983000
C -2.64713100 1.29863400 0.35514300
C -2.63978800 -1.30233900 0.36301800
C -1.23916600 -2.38379500 -1.16102300
C -1.24344300 2.37755200 -1.16813500
C -2.16364700 3.36838500 -0.88036200
C -2.15561300 -3.37559900 -0.86530500
S -3.36163500 2.88739900 0.24926800
S -3.35012300 -2.89337900 0.26720900
41
H -0.44885400 2.49557500 -1.89220600
H -0.44988800 -2.50410000 -1.89040400
H -2.20273200 4.36332700 -1.30331000
H -2.19396100 -4.37219300 -1.28437800
C 0.64608600 0.00691500 -0.24599000
C 1.35750600 1.23607000 -0.08378500
C 1.38538400 -1.21082700 -0.14252500
C 2.74888500 -1.18181000 0.00026400
C 2.72499300 1.23936800 0.05819500
C 3.48135900 0.03922700 0.08557000
H 0.88612900 -2.16740100 -0.15390700
H 0.83146300 2.17795000 -0.04350000
H 3.27360500 -2.12702300 0.06683100
H 3.22213100 2.19298800 0.17485300
C 4.99200700 0.01397800 0.23402200
C 5.36270300 -0.79093400 1.51112100
H 5.01367000 -1.82582700 1.46951300
H 6.45196500 -0.81073400 1.60882300
H 4.94629700 -0.32124000 2.40667700
C 5.60274300 1.42268200 0.34104700
H 5.39773600 2.02745300 -0.54765900
H 5.23881400 1.95941300 1.22257000
H 6.68820500 1.33603800 0.43490500
C 5.59096700 -0.70131000 -1.01086600
H 5.35565500 -0.15641900 -1.92948800
H 6.67897600 -0.74010700 -0.90307900
H 5.22820000 -1.72704500 -1.11450700
Sum of electronic and zero-point Energies= -1944.723518 Sum of electronic and thermal Energies= -1944.703741 Sum of electronic and thermal Enthalpies= -1944.702797 Sum of electronic and thermal Free Energies= -1944.772729