Radical cation and dication of a 4H-dithieno[2,3-b:3',2'-e][1,4]thiazine

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2017 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 a Institut für Organische Chemie und Makromolekulare Chemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany b Institut für Anorganische Chemie und Analytische Chemie, Johannes-Gutenberg-Universität Mainz, Duesbergweg 10-14, D-55128 Mainz, Germany c Institut für Anorganische Chemie und Strukturchemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany Email: ThomasJJ.Mueller@hhu.de 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 4 1 H, 13 C and HSQC NMR spectra of 4-(4-(tert-butyl)phenyl)-4H-dithieno[2,3-b:3',2'-e][1,4]thiazine (5)... 6 1 H NMR of 5 2+ 2 [SbCl 6 ] -... 9 5 Crystal Structure determination of 5... 10 6 UV/Vis spectra of 5 + and 5 2+... 12 7 Computed xyz-coordinates and computed UV/Vis spectra of TD-DFT calculated structures... 14 7.1 XYZ-coordinates for of the S 0 state of the intra conformer of 5 (RB3LYP/6-311G(d))... 14 7.2 XYZ-coordinates for of the S 0 state of the intra conformer of 5 (RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)... 15 7.3 XYZ-coordinates for of the S 0 state of the extra conformer of 5 (RB3LYP/6-311G(d))... 17 7.4 XYZ-coordinates for of the S 0 state of the extra conformer of 5 (RB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)... 18 7.5 XYZ-coordinates for of the S 0 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 D 0 state of 5 + and TD DFT calculation (UB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)... 23 7.7 XYZ-coordinates for of the S 0 state of 5 2+ (UB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)... 29 7.8 XYZ-coordinates for of the T 0 state of 5 2+ (UB3LYP/6-31G(d,p), SCRF(IEFPCM, DCM)... 40

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 λ max,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. 1 H, 13 C and 135-DEPT NMR spectra were recorded on Bruker Avance III 600, Bruker Avance DRX 500, or Bruker Avance III 300 in acetone-d 6 ( 1 H δ 2.05, 13 C δ 29.8) and in CDCl 3 ( 1 H δ 7.26, 13 C δ 77.0). As an internal standard for the 1 H NMR the signal of the remaining protons of the deuterated solvent was used. As internal standard for the 13 C NMR the signal of CDCl 3 (δ 77.0) or acetone-d 6 (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 CH 2 Cl 2 at room temperature and at scan rates of 100, 250, 500 and 1000 mvs -1. The electrolyte was n Bu 4 NPF 6 (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 0/+1 decamethylferrocene in CH 2 Cl 2 (E 0 = -95 mv vs. ferrocene E 0/+1 0 = 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/AgNO 3 reference electrode. As electrolyte 0.1 M solution of [ n Bu 4 N][B(C 6 F 5 ) 4 ] in CH 2 Cl 2 was used. All potentials are stated 1 P. Zanello, Ferrocenes, eds. A. Togni, T. Hayashi, VCH, Weinheim, 1995, 317-430. 2

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 Mn 2+ 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. 3

2 Preparation of starting materials 2.1 Bis(phenylsulfonyl)sulfide 3 28 g (170 mmol) sodium benzenesulfinate were suspended in 250 ml dry diethyl ether. A solution of 9.3 g (90 mmol) sulfur dichloride 4 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. 1 H-NMR (300 MHz, CDCl 3 ): δ 7.63 7.53 (m, 4 H), 7.74 7.66 (m, 2 H), 8.07 7.96 (m, 4 H). 13 C-NMR (75 MHz, CDCl 3 ): δ 128.2 (CH), 129.5 (CH), 135.0 (CH), 144.5 (C quart ). EI-MS (m/z (%)): 250 ([C 12 H 10 S 3 ] +, 14), 141 ([C 6 H 5 O 2 S] +, 78), 125 ([C 6 H 5 OS] +, 16), 109 ([C 6 H 5 S] +, 9), 77 ([C 6 H 5 ] +, 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. 4

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. 1 H-NMR (300 MHz, CDCl 3 ): δ 7.00 (d, 3 J = 5.5 Hz, 2 H), 7.34 (d, 3 J = 5.5 Hz, 2 H). 13 C-NMR (75 MHz, acetone-d 6 ): δ 118.2 (C quart ), 130.3 (C quart ), 131.8 (CH), 132.1 (CH). EI-MS (m/z (%)): 358 ([C 8 H 81 4 Br 2 S 3 ] +, 12), 356 ([C 8 H 79 4 Br 81 BrS 3 ] +, 21), 354 ([C 8 H 79 4 Br 2 S 3 ] +, 10), 196 ([C 8 H 4 S 3 ] +, 100), 82 ([C 4 H 2 S] +, 5). 5

3 1 H, 13 C and HSQC NMR spectra of 4-(4-(tert-butyl)phenyl)-4Hdithieno[2,3-b:3',2'-e][1,4]thiazine (5) 1 H NMR spectra of 5 (acetone-d 6 /CS 2, 300 MHz, 293 K). 6

1 H-NMR spectra of 5 (acetone-d 6, 300 MHz, 293 K). 13 C NMR spectra of 5 (acetone-d 6 /CS 2, 75 MHz, 293 K). 7

HSQC spectra of 5 (benzene-d 6, 300/75 MHz, 293 K). 8

4 1 H NMR of 5 2+ 2 [SbCl 6 ] - 1 H NMR spectra of 5 2+ 2 [SbCl 6 ] - (acetone-d 6, 300 MHz, 293 K). 9

5 Crystal Structure determination of 5 Identification code 5 (exp_1123) Empirical formula C 18 H 17 N S 3 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 [Å 3 ] 1690.6 (8) Formula units Z 4 Calculated density [Mg/m 3 ] 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 [R int = 0.107] Observed reflections [I > 2σ(I)] 4740 Refinement method Full matrix least square on F 2 Absorption correction multi scan : T min = 0.616, T max : 1.000: Data / restraints / parameters 6998 / 0 / 407 Final R indices [I > 2σ(I)] [a,b] R 1 = 0.0668, wr 2 = 0.1532 Goodness-of-fit on F 2[c] 1.198 Largest diff. Peak and hole (max.,min.) [e.ǻ -3 ] 0.54 und -0.42 Completeness [%] 99.9 [a] R 1 = Σ F 0 - F c / Σ F 0 [b] wr 2 = {Σ[w(F 0 2 -F c 2 ) 2 ] / Σ[w(F 0 2 ) 2 ]} 1/2, w = 1/(σ 2 (F 0 2 )+(a P) 2 +b P) (P = [max(0,f 0 2 )+2F c 2 ] 1/3 [c] GooF = S = {[Σw(F 0 2 -F c 2 ) 2 ] / (m-n)} 1/2, m = number of reflections, n = number of parameters 10

Ellipsoid plot 11

6 UV/Vis spectra of 5 + and 5 2+ 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) 12

UV/Vis spectrum of 5 2+ in acetone (c = 4.7 10-4 mol/l; T = 293 K) 13

7 Computed xyz-coordinates and computed UV/Vis spectra of TD- DFT calculated structures 7.1 XYZ-coordinates for of the S 0 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 14

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 S 0 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 15

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 16

7.3 XYZ-coordinates for of the S 0 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 17

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 ΔE intra-extra = - 2.0 kj/mol 7.4 XYZ-coordinates for of the S 0 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 18

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 19

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 ΔE intra-extra = -3.3 kj/mol 7.5 XYZ-coordinates for of the S 0 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 20

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 21

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 22

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 D 0 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 23

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 24

The percentage contributions of a transition to the excited state were calculated by using the following equation 6 : % 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 90A -> 91A 0.15322 85B -> 90B -0.10229 86B -> 90B -0.44651 88B -> 90B 0.86716 Excited State 3:?Spin -A 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 85B -> 90B -0.11936 86B -> 90B 0.26331 87B -> 90B 0.95460 Excited State 5:?Spin -A 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 90A -> 91A 0.15884 85B -> 90B 0.96523 87B -> 90B 0.14512 Excited State 7:?Spin -A 81A -> 92A -0.11273 86A -> 91A -0.41045 86A -> 99A 0.10332 88A -> 92A -0.21196 90A -> 92A 0.71507 81B -> 90B 0.17872 2.4470 ev 506.69 nm f=0.0263 2.4547 ev 505.09 nm f=0.0855 2.6299 ev 471.45 nm f=0.0096 2.7079 ev 457.87 nm f=0.0090 3.0544 ev 405.92 nm f=0.0327 3.4226 ev 362.25 nm f=0.0197 6 R. A. Vogt, T. G. Gray, C. E. Crespo Hernández, J. Am. Chem. Soc. 2012, 134, 14808 14817. 25

81B -> 93B 0.14298 86B -> 91B 0.59581 89B -> 93B 0.19009 Excited State 8:?Spin -A 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 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 90A -> 93A 0.76367 90A -> 94A 0.60554 90A -> 95A -0.13527 90A -> 98A 0.14718 Excited State 11:?Spin -A 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 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 3.7370 ev 331.78 nm f=0.0000 3.8430 ev 322.62 nm f=0.0014 3.8895 ev 318.77 nm f=0.0000 4.1420 ev 299.33 nm f=0.0120 4.2752 ev 290.01 nm f=0.0151 26

Excited State 13:?Spin -A 90A -> 92A -0.10313 81B -> 90B -0.18630 84B -> 90B 0.95933 86B -> 91B 0.11864 Excited State 14:?Spin -A 90A -> 93A -0.63848 90A -> 94A 0.73255 90A -> 95A -0.16204 90A -> 98A 0.13705 Excited State 15:?Spin -A 90A -> 96A 0.98786 Excited State 16:?Spin -A 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 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 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 85A -> 91A 0.35622 86A -> 91A -0.15121 87A -> 91A -0.18347 87A -> 94A 0.14738 87A -> 95A 0.28571 4.2976 ev 288.50 nm f=0.0055 4.3954 ev 282.08 nm f=0.0000 4.4037 ev 281.54 nm f=0.0000 4.5071 ev 275.09 nm f=0.0005 4.5147 ev 274.62 nm f=0.0016 4.5731 ev 271.11 nm f=0.0011 4.6354 ev 267.47 nm f=0.0018 27

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 78B -> 90B -0.11869 82B -> 90B 0.99008 Excited State 21:?Spin -A 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 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 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 4.6422 ev 267.08 nm f=0.0000 4.6513 ev 266.56 nm f=0.0101 4.7029 ev 263.63 nm f=0.0012 4.7574 ev 260.61 nm f=0.3633 28

7.7 XYZ-coordinates for of the S 0 state of 5 2+ (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 29

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. 30

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 31

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 32

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 33

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 34

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 35

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 36

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 37

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 38

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 39

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 T 0 state of 5 2+ (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 40

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 41