Tetrathiafulvalene‐[2.2]paracyclophanes: Synthesis, crystal structures, and chiroptical properties

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Electronic supplementary information (ESI) for:

Tetrathiafulvalene-[2.2.]paracyclophanes: synthesis, crystal structures and chiroptical properties

Cécile Mézière,¹ Magali Allain,¹ Cristina Oliveras-Gonzalez,¹ Thomas Cauchy,¹ Nicolas Vanthuyne,² Laura G. Sarbu,³ Lucian M. Birsa,³ Flavia Pop¹* and Narcis Avarvari¹*

1 Université d'Angers, CNRS, Laboratoire MOLTECH-Anjou, UMR 6200, UFR Sciences, Bât. K, 2 Bd. Lavoisier, 49045 Angers, France. Tel: 33.(0)2.41.73.50.84; Fax: 33.(0)2.41.73.54.05. E- mail: narcis.avarvari@univ-angers.fr

2 Aix Marseille Université, CNRS, Centrale Marseille, iSm2, Marseille, France.

3 Department of Chemistry, “Al. I. Cuza” University of Iasi, 11 Carol I Bv., RO-700506 Iasi, Romania.

FIGURE S1 Packing of (Rp)-1 in the ab plane

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FIGURE S2 Packing of (Rp)-1 in the ac plane

FIGURE S3 Packing of (rac)-2 in the ab plane

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FIGURE S4 Packing of (rac)-2 in the ac plane

FIGURE S5 Packing of (rac)-3 in the ab and bc planes

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FIGURE S6 CD spectra of (Sp)-1 (CD (-)-1 red line) and (Rp)-1 (CD (+)-1 blue line) together with the calculated for (Rp)-1 (CD (+)-1 blue dotted line) and the absorption spectra, experimental (blue line) and calculated (blue dotted

line)

FIGURE S7 CD spectra of (Sp)-2 (CD (-)-2 red line) and (Rp)-2 (CD (+)-2 blue line) together with the calculated for (Rp)-2 (CD (+)-2 blue dotted line) and the absorption spectra, experimental (red line) and calculated (red dotted line)

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Chiral HPLC

Analytical chiral HPLC separation for compound 1

• The sample is dissolved in chloroform, injected on the chiral column, and detected with an UV detector at 254 nm and CD 254nm. The flow-rate is 1 mL/min.

Chiralpak IE

Heptane/ethanol/chloroform 50/30/20

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Semi-preparative separation for compound 1 :

• Sample preparation: About 96 mg of compound 1 are dissolved in 50 mL of a mixture hexane/ethanol/dichloromethane (5/3/2).

• Chromatographic conditions: Chiralpak IE (250 x 10 mm), hexane/ethanol/dichloromethane (5/3/2) as mobile phase, flow-rate = 5 mL/min, UV detection at 254 nm.

• Injection (stacked injections): 250 times 200 l, every 12 minutes.

• Collection: the first eluted enantiomer is collected between 5 and 6 minutes and the second one between 7 and 9 minutes.

• First fraction: 23 mg of the first eluted ((-, CD 254 nm)-enantiomer) with ee > 98.5%

• Second fraction: 20 mg of the second eluted ((+, CD 254 nm)-enantiomer) with ee > 99%

• Chromatograms of the collected enantiomers:

Chiralpak IE

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Analytical chiral HPLC separation for compound 2

• The sample is dissolved in chloroform, injected on the chiral column, and detected with an UV detector at 254 nm and CD 254nm. The flow-rate is 1 mL/min.

Chiralpak IE

(9)

Semi-preparative separation for compound 2:

• Sample preparation: About 90 mg of compound 2 are dissolved in 80 mL of a mixture hexane/ethanol/dichloromethane (5/3/2).

• Chromatographic conditions: Chiralpak IE (250 x 10 mm), hexane/ethanol/dichloromethane (5/3/2) as mobile phase, flow-rate = 5 mL/min, UV detection at 254 nm.

• Injection (stacked injections): 800 times 100 l, every 6 minutes.

• Collection: the first eluted enantiomer is collected between 4 and 5 minutes and the second one between 6 and 7.5 minutes.

• First fraction: 35 mg of the first eluted ((-, CD 254 nm)-enantiomer) with ee > 99%

• Second fraction: 35 mg of the second eluted ((+, CD 254 nm)-enantiomer) with ee > 99%

• Chromatograms of the collected enantiomers:

Chiralpak IE

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Chiralpak IE

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TABLE S1 Excited singlet states calculated wavelengths, oscillator and rotatory strengths and electron density difference plots (where a blue surfaces indicate the excited electron density and the white surfaces indicate the hole) for compound 2

Excitation λmax, calc

(nm)

λmax, exp

(nm)

Oscillator strength

Rotatory strength

EDD plot

S0S1 544 - 0.04 38

S0S3 398 410 0.02 -18

S0S5 330 324 0.02 -27

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Theoretical calculations report compound 1

--- MOLECULAR DESCRIPTION ---

[Molecular formula]

C24H20S6

[Number of atoms]

50

[Monoisotopic mass] (in Daltons) 499.9889308

[Charge]

0

[Multiplicity]

1

[Full point group]

C1

--- COMPUTATIONAL DETAILS --- [Method]

PBE1PBE [Standard basis]

6-311++G(2df,2pd) (5D, 7F) [Number of basis functions]

1368

[Solvent effects]

None [Solvent]

Gas

[Restricted or Unrestricted calculation]

Closed shell

--- SCF parameters ---

[Requested convergence on RMS density matrix]

1.00E-08

[Requested convergence on Max density matrix]

1.00E-06

[Requested convergence on Energy] (in Hartrees) 1.00E-06

--- Optimization parameters ---

[Maximum Force Threshold]

0.00045

[RMS Force Threshold]

(13)

0.0003

[Maximum Displacement Threshold]

0.0018

[RMS Displacement Threshold]

0.0012

--- Time-Dependant parameters ---

[Number of computed singlet excited states]

15

--- RESULTS ---

--- Equilibrium Ground State geometry and energies ---

[Nuclear repulsion] (in Hartrees) 3884.0308102010

[Maximum Force Value]

2e-05

[RMS Force Value]

3e-06

[Maximum Displacement Value]

0.001299

[RMS Displacement Value]

0.000357

[Converged optimization]

True

[Stationary point]

Yes

[Molecular electronic energy] (in Hartrees) -90181.694986

[Five lowest normal modes vibrational frequencies] (in wavenumbers) 16

22 27 28 43

[Converged Cartesian atomic positions] (in Angstroms) Atom Atomic n° X Y Z

1 6 -1.15092 -1.01354 -0.04278 2 6 -2.40458 -0.57750 -0.25773 3 16 -0.75999 -2.68578 0.30616 4 16 0.25288 0.02832 -0.13726 5 16 -3.80866 -1.62745 -0.23025 6 16 -2.80158 1.08266 -0.65055 7 6 0.86927 -2.34700 0.79875 8 6 1.36806 -1.11996 0.60479 9 6 -4.92232 -0.30971 0.11951 10 6 -4.45751 0.93382 -0.07753

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11 1 1.42263 -3.15305 1.25926 12 6 2.71561 -0.66910 0.96712 13 16 -6.51552 -0.81533 0.60379 14 16 -5.42913 2.37627 -0.00334 15 6 3.85295 -1.46887 0.73987 16 6 2.89546 0.62942 1.44707 17 6 -7.56782 0.63210 0.23441 18 6 -6.94711 1.65732 -0.68386 19 6 5.03404 -1.05611 1.34998 20 6 3.95072 -2.51542 -0.34423 21 6 4.15171 1.14000 1.75766 22 1 2.03572 1.29059 1.47948 23 1 -8.47046 0.21742 -0.22114 24 1 -7.83737 1.09282 1.18351 25 1 -7.63763 2.49300 -0.81252 26 1 -6.71924 1.24152 -1.66556 27 1 5.90655 -1.69635 1.27636 28 6 5.18807 0.22028 1.86608 29 6 3.98635 -1.89603 -1.80129 30 1 3.14233 -3.24466 -0.32179 31 1 4.87736 -3.06992 -0.18436 32 6 4.41152 2.62102 1.71485 33 1 6.16761 0.54158 2.20326 34 6 4.42499 -0.45770 -1.82079 35 1 4.63633 -2.52941 -2.41012 36 1 2.98380 -1.96387 -2.22777 37 1 5.05690 2.93369 2.53901 38 1 3.46507 3.15094 1.83613 39 6 5.08706 3.09557 0.35865 40 6 5.73168 -0.07970 -1.52314 41 6 3.47095 0.55699 -1.86899 42 1 4.63224 4.04756 0.07545 43 1 6.14419 3.29272 0.54693 44 6 4.96262 2.07558 -0.73877 45 6 5.99363 1.17071 -0.98416 46 1 6.52980 -0.81364 -1.56830 47 1 2.46248 0.32281 -2.19237 48 6 3.73491 1.80934 -1.33856 49 1 6.99081 1.38864 -0.61589 50 1 2.92715 2.52955 -1.25771

--- Electron density ---

[Number of molecular orbitals]

1361

[HOMO is number]

129

[Calculated energies of frontier orbitals] (in eV)

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LUMO+2 -0.77 LUMO+1 -0.98 LUMO -1.42 HOMO -4.94 HOMO-1 -6.03 HOMO-2 -6.44

[Mulliken charges with hydrogens summed into heavy atoms] (in electrons) 1 C 1.06

2 C 1.24 3 S -0.91 4 S -1.18 5 S -0.84 6 S -0.93 7 C 1.36 8 C -0.17 9 C 0.99 10 C 1.05 12 C 0.31 13 S -0.95 14 S -0.84 15 C 0.20 16 C -0.37 17 C 0.36 18 C 0.13 19 C -0.29 20 C -0.16 21 C 0.37 28 C -0.29 29 C -0.10 32 C -0.08 34 C 0.36 39 C -0.32 40 C 0.01 41 C -0.19 44 C 0.39 45 C -0.07 48 C -0.15

[Hirshfeld charges, spin densities, dipoles, and CM5 charges] (in electrons) Q-H S-H Dx Dy Dz Q-CM5

1 C -0.06 0.00 0.08 -0.03 0.01 -0.09 2 C -0.07 0.00 -0.07 0.02 -0.01 -0.10 3 S 0.05 0.00 0.03 -0.02 0.03 0.04 4 S 0.06 0.00 0.05 0.01 0.01 0.05 5 S 0.03 0.00 0.01 -0.01 0.02 0.03 6 S 0.03 0.00 0.01 0.00 0.02 0.03 7 C -0.07 0.00 0.00 -0.11 0.03 -0.11

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8 C -0.02 0.00 0.06 0.09 -0.01 -0.02 9 C -0.06 0.00 -0.04 -0.08 0.02 -0.06 10 C -0.07 0.00 0.03 0.09 -0.01 -0.07 11 H 0.07 0.00 0.09 -0.14 0.08 0.13 12 C -0.01 0.00 -0.04 -0.03 -0.01 -0.02 13 S 0.01 0.00 -0.07 0.09 -0.02 -0.00 14 S 0.01 0.00 -0.06 -0.02 -0.02 -0.00 15 C -0.00 0.00 -0.02 -0.05 -0.04 -0.02 16 C -0.05 0.00 -0.03 0.03 0.01 -0.10 17 C -0.06 0.00 -0.02 -0.01 -0.01 -0.15 18 C -0.06 0.00 -0.03 0.00 -0.01 -0.15 19 C -0.05 0.00 0.05 -0.03 -0.00 -0.10 20 C -0.06 0.00 -0.00 0.02 -0.02 -0.16 21 C -0.00 0.00 0.01 0.07 0.01 -0.02 22 H 0.04 0.00 -0.10 0.10 0.03 0.10 23 H 0.05 0.00 -0.13 -0.06 -0.09 0.11 24 H 0.05 0.00 -0.08 0.08 0.13 0.11 25 H 0.06 0.00 -0.12 0.12 -0.04 0.12 26 H 0.06 0.00 0.03 -0.06 -0.16 0.11 27 H 0.05 0.00 0.13 -0.09 -0.01 0.10 28 C -0.05 0.00 0.06 0.02 0.02 -0.10 29 C -0.06 0.00 0.01 -0.00 0.02 -0.16 30 H 0.04 0.00 -0.10 -0.11 -0.01 0.09 31 H 0.04 0.00 0.13 -0.09 0.01 0.09 32 C -0.06 0.00 0.01 -0.00 -0.03 -0.16 33 H 0.05 0.00 0.15 0.04 0.05 0.11 34 C -0.01 0.00 -0.01 -0.07 -0.02 -0.02 35 H 0.04 0.00 0.09 -0.09 -0.09 0.10 36 H 0.04 0.00 -0.14 -0.02 -0.06 0.10 37 H 0.04 0.00 0.10 0.04 0.11 0.10 38 H 0.04 0.00 -0.13 0.08 0.02 0.10 39 C -0.06 0.00 -0.02 -0.01 0.02 -0.16 40 C -0.05 0.00 0.04 -0.04 -0.01 -0.11 41 C -0.05 0.00 -0.04 -0.01 -0.03 -0.11 42 H 0.04 0.00 -0.07 0.14 -0.03 0.10 43 H 0.04 0.00 0.15 0.03 0.03 0.09 44 C -0.01 0.00 0.01 0.06 0.04 -0.03 45 C -0.05 0.00 0.05 0.01 0.02 -0.11 46 H 0.05 0.00 0.12 -0.11 -0.01 0.10 47 H 0.04 0.00 -0.12 -0.02 -0.06 0.10 48 C -0.05 0.00 -0.04 0.05 0.00 -0.10 49 H 0.04 0.00 0.15 0.02 0.05 0.10 50 H 0.05 0.00 -0.12 0.11 0.02 0.10

--- Thermochemistry and normal modes ---

[Temperature] (in Kelvins) 298.15

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[Sum of electronic and zero-point Energies] (in Hartree/molecule) 3313.739368

[Sum of electronic and thermal Energies] (in Hartree/molecule) 3313.712458

[Sum of electronic and thermal Enthalpies] (in Hartree/molecule) -3313.711514

[Sum of electronic and thermal Free Energies] (in Hartree/molecule) 3313.799340

--- Infrared Spectroscopy ---

[Most intense normal modes IR intensities > 10 km/mol]

cm-1 km/mol 531 13.4 671 20.6 745 12.6 753 13.4 756 15.0 798 16.3 805 39.2 810 18.7 825 10.9 827 21.7 922 16.4 928 19.7 935 16.1 950 10.7 1322 29.1 1473 10.0 1530 12.9 1641 24.1 1655 23.7 3057 12.1 3059 25.5 3068 12.2 3068 73.0 3077 34.4 3079 20.0 3107 15.4 3120 21.2 3134 23.1 3185 14.2 3191 17.1

--- CDFT Values --- Eref = -3314.116309 h

Eplus = -3314.128616 h Emoins = -3313.891043 h I = 6.129803 eV

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A = 0.334880 eV Khi = 3.232342 eV Eta = 5.794922 eV deltaN = 0.557789 Omega = 0.901482 eV

--- Excited states and UV-visible spectroscopy ---

[Excited singlet states calculated energies, symmetries, oscillator and rotatory strengths]

Exitation cm-1 Symmetry Osc. strength Rot. strength Λ dCT(pm) qCT(e-) ||μCT||(D) S0->S 1 21610 Singlet-A 0.013 -11.015 0.51 467 0.64 14.3

S0->S 2 23364 Singlet-A 0.064 -61.730 0.53 388 0.62 11.6 S0->S 3 28102 Singlet-A 0.011 26.686 0.47 293 0.59 8.3 S0->S 4 28652 Singlet-A 0.028 -43.862 0.50 165 0.60 4.7 S0->S 5 30338 Singlet-A 0.191 -24.302 0.64 215 0.38 3.9 S0->S 6 31380 Singlet-A 0.021 8.289 0.46 116 0.54 3.0 S0->S 7 32087 Singlet-A 0.087 79.655 0.62 399 0.39 7.5 S0->S 8 32505 Singlet-A 0.070 -38.842 0.47 334 0.42 6.8 S0->S 9 32714 Singlet-A 0.036 -9.363 0.35 656 0.64 20.2 S0->S10 33001 Singlet-A 0.025 -58.502 0.49 223 0.46 5.0 S0->S11 33232 Singlet-A 0.149 -8.205 0.41 254 0.60 7.3 S0->S12 33845 Singlet-A 0.014 60.905 --- --- --- --- S0->S13 34308 Singlet-A 0.005 -7.169 --- --- --- --- S0->S14 34702 Singlet-A 0.008 16.410 --- --- --- --- S0->S15 35013 Singlet-A 0.028 -30.564 0.46 219 0.51 5.4 [Excited singlet states principal singly-excited configurations for all calculated electronic transitions > 10% ]

S0 --> S 1 55% HOMO --> LUMO S0 --> S 1 37% HOMO --> LUMO+1 S0 --> S 2 41% HOMO --> LUMO S0 --> S 2 54% HOMO --> LUMO+1 S0 --> S 3 48% HOMO --> LUMO+2 S0 --> S 3 33% HOMO --> LUMO+3 S0 --> S 4 38% HOMO --> LUMO+2 S0 --> S 4 53% HOMO --> LUMO+3 S0 --> S 5 13% HOMO -1 --> LUMO S0 --> S 5 18% HOMO -1 --> LUMO+1 S0 --> S 5 48% HOMO --> LUMO+4 S0 --> S 6 34% HOMO --> LUMO+7 S0 --> S 6 31% HOMO --> LUMO+8 S0 --> S 7 33% HOMO -1 --> LUMO S0 --> S 7 33% HOMO --> LUMO+4 S0 --> S 8 35% HOMO -2 --> LUMO S0 --> S 8 15% HOMO -1 --> LUMO S0 --> S 8 16% HOMO --> LUMO+5 S0 --> S 9 14% HOMO -1 --> LUMO S0 --> S 9 57% HOMO --> LUMO+5 S0 --> S10 46% HOMO -2 --> LUMO

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S0 --> S10 14% HOMO -1 --> LUMO S0 --> S10 12% HOMO --> LUMO+5 S0 --> S11 68% HOMO --> LUMO+6 S0 --> S12 28% HOMO --> LUMO+7 S0 --> S12 46% HOMO --> LUMO+8 S0 --> S13 24% HOMO -1 --> LUMO+1 S0 --> S13 12% HOMO --> LUMO+9 S0 --> S13 36% HOMO --> LUMO+12 S0 --> S14 11% HOMO -4 --> LUMO S0 --> S14 42% HOMO -3 --> LUMO S0 --> S14 15% HOMO --> LUMO+11 S0 --> S15 36% HOMO --> LUMO+11 S0 --> S15 21% HOMO --> LUMO+12

(20)

Theoretical calculations report of compound 2

--- MOLECULAR DESCRIPTION ---

[Molecular formula]

C26H22O4S4 [Number of atoms]

56

[Monoisotopic mass] (in Daltons) 526.0400956

[Charge]

0

[Multiplicity]

1

[Full point group]

C1

--- COMPUTATIONAL DETAILS --- [Method]

PBE1PBE [Standard basis]

6-311++G(2df,2pd) (5D, 7F) [Number of basis functions]

1518

[Solvent effects]

None [Solvent]

Gas

[Restricted or Unrestricted calculation]

Closed shell

--- SCF parameters ---

[Requested convergence on RMS density matrix]

1.00E-08

[Requested convergence on Max density matrix]

1.00E-06

[Requested convergence on Energy] (in Hartrees) 1.00E-06

--- Optimization parameters ---

[Maximum Force Threshold]

0.00045

[RMS Force Threshold]

(21)

0.0003

[Maximum Displacement Threshold]

0.0018

[RMS Displacement Threshold]

0.0012

--- Time-Dependant parameters ---

[Number of computed singlet excited states]

15

--- RESULTS ---

--- Equilibrium Ground State geometry and energies ---

[Nuclear repulsion] (in Hartrees) 4244.2128787025

[Maximum Force Value]

5e-06

[RMS Force Value]

1e-06

[Maximum Displacement Value]

0.000769

[RMS Displacement Value]

0.000182

[Converged optimization]

True

[Stationary point]

Yes

[Molecular electronic energy] (in Hartrees) -78805.029067

[Five lowest normal modes vibrational frequencies] (in wavenumbers) 11

15 21 26 36

[Converged Cartesian atomic positions] (in Angstroms) Atom Atomic n° X Y Z

1 6 2.01284 -0.88826 -0.68191 2 6 0.75463 -1.36280 -0.67264 3 16 2.39103 0.78387 -1.05275 4 16 3.42115 -1.87895 -0.34655 5 16 -0.64792 -0.37605 -1.02823 6 16 0.37228 -3.03484 -0.30681 7 6 3.98939 0.71116 -0.37315 8 6 4.47025 -0.50400 -0.06153 9 6 -1.83343 -1.55894 -0.47629 10 6 -1.33458 -2.75977 -0.16113

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11 6 4.68459 2.02897 -0.27717 12 6 5.82859 -0.86461 0.37790 13 6 -3.25290 -1.18726 -0.47325 14 1 -1.94760 -3.60277 0.12560 15 8 4.91308 2.71982 -1.23134 16 8 4.93701 2.36014 0.98294 17 8 6.12966 -1.98607 0.69939 18 8 6.68362 0.15733 0.33831 19 6 -4.10081 -1.51062 0.60430 20 6 -3.74739 -0.40105 -1.51686 21 6 5.59636 3.61304 1.15769 22 6 8.01565 -0.15370 0.73825 23 6 -5.46588 -1.33933 0.39349 24 6 -3.60186 -1.71790 2.01357 25 6 -5.06465 0.03830 -1.54110 26 1 -3.05320 -0.04045 -2.26941 27 1 6.56608 3.60227 0.66013 28 1 5.71678 3.73519 2.23035 29 1 4.99454 4.42171 0.74386 30 1 8.03277 -0.50174 1.77088 31 1 8.57775 0.77062 0.63644 32 1 8.43472 -0.92793 0.09621 33 1 -6.15942 -1.66744 1.16065 34 6 -5.94608 -0.58373 -0.66078 35 1 -2.53438 -1.92690 2.00030 36 1 -4.08530 -2.58112 2.47772 37 6 -3.85253 -0.46229 2.95063 38 6 -5.47844 1.28124 -2.27843 39 1 -7.00471 -0.35386 -0.71015 40 1 -4.71438 -0.66480 3.58947 41 1 -2.98594 -0.37078 3.60995 42 6 -4.10176 0.80749 2.18377 43 6 -5.15460 2.61982 -1.48145 44 1 -6.55322 1.24470 -2.46582 45 1 -4.98845 1.33964 -3.25245 46 6 -5.39285 1.30618 2.02529 47 6 -3.10678 1.36886 1.38712 48 6 -4.77421 2.36854 -0.04967 49 1 -4.33471 3.13086 -1.98948 50 1 -6.02775 3.27198 -1.55047 51 1 -6.18018 0.96551 2.68984 52 6 -5.72690 2.08091 0.92382 53 6 -3.44127 2.13482 0.28335 54 1 -2.07033 1.08366 1.53498 55 1 -6.76793 2.33304 0.74970 56 1 -2.65895 2.43411 -0.40635

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--- Electron density ---

[Number of molecular orbitals]

1510

[HOMO is number]

136

[Calculated energies of frontier orbitals] (in eV) LUMO+2 -1.08

LUMO+1 -1.37 LUMO -1.97 HOMO -5.11 HOMO-1 -6.42 HOMO-2 -6.49

[Mulliken charges with hydrogens summed into heavy atoms] (in electrons) 1 C 1.43

2 C 0.99 3 S -1.08 4 S -0.68 5 S -1.25 6 S -0.96 7 C 0.32 8 C 1.25 9 C -0.11 10 C 1.57 11 C -0.30 12 C -0.47 13 C 0.10 15 O -0.30 16 O 0.02 17 O -0.33 18 O -0.11 19 C 0.50 20 C -0.31 21 C 0.25 22 C 0.24 23 C -0.16 24 C -0.28 25 C 0.41 34 C -0.32 37 C -0.22 38 C -0.36 42 C 0.37 43 C -0.11 46 C 0.00 47 C -0.18 48 C 0.40 52 C 0.01

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53 C -0.35

[Hirshfeld charges, spin densities, dipoles, and CM5 charges] (in electrons) Q-H S-H Dx Dy Dz Q-CM5

1 C -0.08 0.00 0.07 0.03 -0.01 -0.10 2 C -0.06 0.00 -0.08 -0.03 -0.01 -0.09 3 S 0.07 0.00 -0.01 0.02 -0.02 0.07 4 S 0.06 0.00 0.00 -0.02 0.02 0.06 5 S 0.05 0.00 -0.04 0.01 0.01 0.05 6 S 0.05 0.00 -0.03 -0.03 0.01 0.04 7 C -0.02 0.00 0.00 0.09 -0.00 -0.00 8 C -0.03 0.00 0.06 -0.06 0.03 -0.01 9 C -0.02 0.00 -0.06 0.09 -0.01 -0.01 10 C -0.07 0.00 -0.00 -0.11 0.04 -0.11 11 C 0.21 0.00 0.05 0.00 0.07 0.28 12 C 0.21 0.00 0.07 0.07 -0.00 0.27 13 C -0.01 0.00 0.04 -0.03 0.01 -0.02 14 H 0.07 0.00 -0.10 -0.15 0.04 0.13 15 O -0.27 0.00 0.01 -0.03 0.05 -0.32 16 O -0.12 0.00 0.02 0.09 -0.04 -0.20 17 O -0.27 0.00 0.00 0.06 -0.02 -0.32 18 O -0.12 0.00 0.05 -0.06 0.04 -0.20 19 C -0.00 0.00 0.03 -0.03 0.05 -0.02 20 C -0.05 0.00 0.02 0.02 -0.04 -0.10 21 C -0.01 0.00 -0.02 -0.05 0.01 -0.13 22 C -0.01 0.00 -0.04 0.03 -0.02 -0.13 23 C -0.05 0.00 -0.04 -0.02 0.04 -0.10 24 C -0.06 0.00 -0.02 0.03 0.01 -0.16 25 C -0.00 0.00 -0.02 0.05 -0.04 -0.02 26 H 0.04 0.00 0.08 0.06 -0.11 0.10 27 H 0.05 0.00 0.13 0.03 -0.10 0.11 28 H 0.06 0.00 0.07 -0.00 0.15 0.12 29 H 0.05 0.00 -0.09 0.13 0.01 0.12 30 H 0.05 0.00 0.03 -0.02 0.16 0.12 31 H 0.06 0.00 0.10 0.12 -0.04 0.12 32 H 0.05 0.00 0.07 -0.12 -0.08 0.12 33 H 0.05 0.00 -0.11 -0.05 0.11 0.11 34 C -0.05 0.00 -0.06 0.01 -0.01 -0.10 35 H 0.03 0.00 0.14 -0.02 0.02 0.09 36 H 0.04 0.00 -0.07 -0.12 0.07 0.10 37 C -0.06 0.00 0.01 -0.01 -0.02 -0.16 38 C -0.06 0.00 0.01 0.02 0.02 -0.16 39 H 0.05 0.00 -0.16 0.03 -0.00 0.11 40 H 0.04 0.00 -0.12 -0.04 0.09 0.09 41 H 0.04 0.00 0.12 0.01 0.10 0.10 42 C -0.01 0.00 0.02 -0.05 0.05 -0.02 43 C -0.06 0.00 -0.01 -0.03 -0.01 -0.16

(25)

44 H 0.04 0.00 -0.15 0.00 -0.03 0.10 45 H 0.04 0.00 0.07 0.02 -0.14 0.10 46 C -0.05 0.00 -0.04 -0.02 0.04 -0.11 47 C -0.05 0.00 0.05 -0.01 0.02 -0.10 48 C -0.01 0.00 -0.02 0.03 -0.06 -0.03 49 H 0.04 0.00 0.12 0.07 -0.07 0.10 50 H 0.04 0.00 -0.12 0.10 -0.02 0.10 51 H 0.04 0.00 -0.12 -0.05 0.09 0.10 52 C -0.05 0.00 -0.06 0.02 -0.01 -0.11 53 C -0.05 0.00 0.04 0.03 -0.03 -0.10 54 H 0.05 0.00 0.14 -0.03 0.04 0.10 55 H 0.05 0.00 -0.15 0.03 -0.03 0.10 56 H 0.05 0.00 0.11 0.05 -0.09 0.10

--- Thermochemistry and normal modes ---

[Temperature] (in Kelvins) 298.15

[Sum of electronic and zero-point Energies] (in Hartree/molecule) 2895.607934

[Sum of electronic and thermal Energies] (in Hartree/molecule) 2895.575937

[Sum of electronic and thermal Enthalpies] (in Hartree/molecule) -2895.574993

[Sum of electronic and thermal Free Energies] (in Hartree/molecule) 2895.675617

--- Infrared Spectroscopy ---

[Most intense normal modes IR intensities > 10 km/mol]

cm-1 km/mol 302 15.3 327 11.2 397 10.1 448 10.1 527 16.3 668 22.6 726 46.6 748 27.9 765 10.6 789 40.8 796 20.8 798 14.2 805 10.3 811 17.5 828 21.3 919 24.9 932 11.0 985 34.2

(26)

1094 120.4 1140 43.5 1218 12.3 1311 403.1 1329 917.4 1469 29.9 1473 66.6 1477 12.9 1490 13.4 1493 12.6 1531 13.5 1604 36.9 1635 151.5 1650 55.5 1660 12.6 1793 342.1 1821 248.4 3057 16.3 3059 12.6 3071 13.9 3071 112.2 3071 60.7 3123 22.1 3144 12.3 3150 13.2 3185 19.1 3192 18.2

--- CDFT Values --- Eref = -2896.031530 h

Eplus = -2896.059911 h Emoins = -2895.798343 h I = 6.345337 eV A = 0.772298 eV Khi = 3.558818 eV Eta = 5.573039 eV deltaN = 0.638578 Omega = 1.136291 eV

--- Excited states and UV-visible spectroscopy ---

[Excited singlet states calculated energies, symmetries, oscillator and rotatory strengths]

Exitation cm-1 Symmetry Osc. strength Rot. strength Λ dCT(pm) qCT(e-) ||μCT||(D) S0->S 1 18372 Singlet-A 0.036 37.981 0.46 432 0.76 15.7

S0->S 2 21815 Singlet-A 0.001 -8.905 0.55 329 0.63 10.0 S0->S 3 25155 Singlet-A 0.018 -17.663 0.56 280 0.62 8.4 S0->S 4 28638 Singlet-A 0.009 -0.160 0.30 573 0.81 22.3 S0->S 5 30889 Singlet-A 0.023 -27.212 0.52 313 0.53 8.0 S0->S 6 31321 Singlet-A 0.007 2.652 --- --- --- ---

(27)

S0->S 7 31920 Singlet-A 0.124 30.532 --- --- --- --- S0->S 8 32587 Singlet-A 0.005 15.491 --- --- --- --- S0->S 9 32795 Singlet-A 0.050 -41.209 0.53 237 0.42 4.8 S0->S10 33696 Singlet-A 0.057 0.325 0.44 696 0.56 18.6 S0->S11 34361 Singlet-A 0.296 -206.129 0.53 316 0.39 5.9 S0->S12 34697 Singlet-A 0.052 60.549 --- --- --- --- S0->S13 34907 Singlet-A 0.029 -15.834 --- --- --- --- S0->S14 35380 Singlet-A 0.083 -2.439 0.36 266 0.60 7.7 S0->S15 35551 Singlet-A 0.014 -13.606 --- --- --- —

[Excited singlet states principal singly-excited configurations for all calculated electronic transitions > 10% ]

S0 --> S 1 97% HOMO --> LUMO

S0 --> S 2 57% HOMO --> LUMO+1 S0 --> S 2 37% HOMO --> LUMO+2 S0 --> S 3 40% HOMO --> LUMO+1 S0 --> S 3 56% HOMO --> LUMO+2 S0 --> S 4 92% HOMO --> LUMO+3 S0 --> S 5 31% HOMO --> LUMO+5 S0 --> S 5 45% HOMO --> LUMO+6 S0 --> S 6 60% HOMO -1 --> LUMO S0 --> S 6 11% HOMO --> LUMO+4 S0 --> S 7 23% HOMO -1 --> LUMO S0 --> S 7 59% HOMO --> LUMO+4 S0 --> S 8 51% HOMO -2 --> LUMO S0 --> S 8 22% HOMO -2 --> LUMO+1 S0 --> S 9 14% HOMO --> LUMO+4 S0 --> S 9 38% HOMO --> LUMO+5 S0 --> S 9 14% HOMO --> LUMO+6 S0 --> S10 30% HOMO -2 --> LUMO S0 --> S10 13% HOMO -2 --> LUMO+1 S0 --> S10 31% HOMO -1 --> LUMO+1 S0 --> S11 33% HOMO -2 --> LUMO+1 S0 --> S11 21% HOMO -1 --> LUMO+1 S0 --> S12 12% HOMO -1 --> LUMO+1 S0 --> S12 10% HOMO --> LUMO+6 S0 --> S12 12% HOMO --> LUMO+7 S0 --> S12 11% HOMO --> LUMO+9 S0 --> S12 12% HOMO --> LUMO+10 S0 --> S12 12% HOMO --> LUMO+11 S0 --> S13 31% HOMO --> LUMO+7 S0 --> S13 14% HOMO --> LUMO+8 S0 --> S14 18% HOMO --> LUMO+7 S0 --> S14 26% HOMO --> LUMO+8 S0 --> S14 17% HOMO --> LUMO+12 S0 --> S15 59% HOMO -3 --> LUMO S0 --> S15 14% HOMO -3 --> LUMO+1