Supporting Information For:

Supporting Information For: Highly Fluorinated Ir(III)- 2,2 :6,2 -Terpyridine -Phenylpyridine-X Complexes via Selective C-F Activation: Robust Photocatalysts for Solar Fuel Generation and Photoredox Catalysis Jonathan A. Porras, Isaac N. Mills, Wesley J. Transue, and Stefan Bernhard Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States Synthesis and Characterization of mppy Precursors Synthesis and Characterization of mppy Ligands NMR Spectra of Final Complexes NMR Spectra of Crude Reactions and Derivatizations ESI-MS of Crude Reactions UV-Vis Absorption Spectra TD-DFT Results Computational Emission Energy Modeling Additional Photoredox Catalysis CO 2 Traces Combined Triplet Orbital Diagrams (3a-3c) Expanded Frontier Orbital Diagrams Calculated Molecular Orbitals and Singlet Optimized Geometries S1-S2 S2-S4 S5-S18 S18-S19 S20 S21 S22-S23 S23 S24 S25 S26-S27 S28-S45

Synthesis of mppy Precursors. In a typical reaction, the corresponding acetophenone (50 mmol) was dissolved in CHCl 3 (40 ml) and cooled to 0 o C with an ice bath. A solution of Br 2 (1.10 equiv) in CHCl 3 was added and the solution was left to stir for 2 hours at room temperature, at which point the solution became pale orange. The reaction mixture was poured into a 250 ml separatory funnel and was washed with saturated Na 2 S 2 O 3, water, and saturated NaCl. The CHCl 3 was evaporated in-vacuo and the orange oil was suspended in diethyl ether. A solution of pyridine (10 equiv) in diethyl ether was added, which upon addition formed an immediate precipitate. The solution was stirred for 3 hours, at which point the precipitate was filtered and washed with diethyl ether. The product was of sufficient purity to use in the next synthetic step. 1-(2-oxo-2-phenylethyl)pyridine-1-ium bromide. 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.04 (dd, J = 1.23, 6.69 Hz, 2H), 8.75 (m,1h), 8.29 (m, 2H), 8.08 (dd, J = 1.23, 8.34, 2H), 7.80 (m, 1H), 7.69 (m, 2H), 6.54 (s, 2H). 1-(2-(4-fluorophenyl)-2-oxoethyl)pyridine-1-ium bromide. 1 H NMR (300 MHz, DMSO-d 6 ): δ. 9.14 (m, 2H), 8.75 (m, 1H), 8.29 (m, 2H), 8.17 (m, 2H), 7.51 (m, 2H), 6.68 (s, 2H). 19 F NMR (282.37 MHz, DMSO-d 6 ): δ -101.53 (m, 1F). 1-(2-(2-fluorophenyl)-2-oxoethyl)pyridin-1-ium bromide. 1 H NMR (300 MHz, DMSO-d 6 ): δ. 9.04 (dd, J = 1.10, 6.56 Hz, 2H), 8.75 (t, J = 7.83 Hz, 1H), 8.29 (m, 2H), 8.02 (td, J = 1.80, 7.67 Hz, 1H), 7.85 (m, 1H), 7.52 (m, 2H), 6.37 (d, J = 3.28 Hz, 2H). 19 F NMR (282.37 MHz, DMSOd 6 ): δ -105.73 (m, 1F). 1-(2-(2,4-difluorophenyl)-2-oxoethyl)pyridin-1-ium bromide. 1 H NMR (300 MHz, DMSOd 6 ): δ. 9.17 (d, J = 5.55 Hz, 2H), 8.75 (t, J = 7.83 Hz, 1H), 8.29 (m, 2H), 8.11 (td, J = 6.70, 8.66 Hz, 1H), 7.62 (ddd, J = 2.40, 9.27, 11.71 Hz, 1H), 7.37 (td, J = 2.35, 8.47, 8.50 Hz, 1H), 6.50 (d, J = 3.11 Hz, 2H). 19 F NMR (282.37 MHz, DMSO-d 6 ): δ -97.73 (m, 1H), -100.91 (m, 1H). S1

1-(2-(2,6-difluorophenyl)-2-oxoethyl)pyridin-1-ium bromide. 1 H NMR (300 MHz, DMSOd 6 ): δ. 9.05 (d, J = 5.47 Hz, 2H), 8.75 (t, J = 7.84 Hz, 1H), 8.29 (m, 2H), 7.84 (tt, J = 6.35, 8.45 Hz, 1H), 7.38 (dd, J = 8.54, 9.95 Hz, 2H), 6.28 (s, 2H). 19 F NMR (282.37 MHz, DMSO-d 6 ): δ - 105.94 (dd, J = 6.60, 10.28, 2F). 1-(2-oxo-2-(2,4,6-trifluorophenyl)ethyl)pyridin-1-ium bromide. 1 H NMR (300 MHz, DMSOd 6 ): δ. 9.05 (d, J = 5.50 Hz, 2H), 8.75 (t, J = 7.84 Hz, 1H), 8.29 (m, 2H), 7.53 (m, 2H), 6.27 (s, 2H). 19 F NMR (282.37 MHz, DMSO-d 6 ): δ -96.151 (m, 1F), -101.91 (t, J = 11.01 Hz, 2F). Synthesis of mppy Ligands by Kröhnke Condensation. In a typical reaction, the corresponding acyl pyridinium bromide precursor (40 mmol), methacrolein (1.05 equiv), NH 4 OAc (10 equiv), and methanol (50 ml) were combined and heated to 65 o C overnight. The solution was diluted with a four-fold volume of water and extracted with diethyl ether. The diethyl ether was removed in vacuo, and the crude residue was dissolved in 3 M HCl (Note: at this step some of the more fluorinated mppy ligands may crash out of solution as their HCl salts). The aqueous layer was extracted twice with diethyl ether, after which it was neutralized with solid Na 2 CO 3. The aqueous phase was extracted with diethyl ether, dried with Na 2 SO 4, and solvent was removed in vacuo. The product was then chromatographed on silica gel using 10% EtOAc/Hexanes as the eluent. 5-methyl-2-phenylpyridine (mppy). Yield: 64%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.53 (m, 1H), 7.98 (m, 2H), 7.62 (d, J = 8.06 Hz, 1H), 7.54 (dd, J = 2.09, 8.07 Hz, 1H), 7.46 (t, J = 7.53 Hz, 2H), 7.39 (t, J = 7.32 Hz, 1H), 2.36 (s, 3H). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 154.80, 150.03, 139.37, 137.45, 131.68, 128.76, 128.69, 126.77, 120.12 (broad, 2C), 120.04, 18.21. MS (m/z ESI, CH 3 OH) Calculated: 170.1 [M+H] + Found: 170.2 [M+H] +. 2-(4-fluorophenyl)-5-methylpyridine (4-Fmppy). Yield: 62%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.50 (s, 1H), 7.94 (ddd, J = 2.58, 5.30, 8.41 Hz, 2H), 7.57 (m, 2H), 7.13 (m, 2H), 2.36 (s, 3H). 19 F NMR (470.54 MHz, CDCl 3 ): δ. -111.72 (s, 1F). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 163.46 S2

(d, J = 247.96 Hz), 153.822, 150.00, 137.66, 135.49 (d, 3.09 Hz), 131.76, 128.62, 128.56, 120.10, 119.90, 115.71 (d, J = 21.61 Hz), 18.24. MS (m/z ESI, CH 3 OH) Calculated: 188.1 [M+H] + Found: 188.2 [M+H] +. 2-(2-fluorophenyl)-5-methylpyridine (2-Fmppy). Yield: 74%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.55 (s, 1H), 7.96 (td, J = 1.79, 7.88 Hz, 1H), 7.68 (dd, J = 2.05, 8.06 Hz, 1H), 7.55 (dd, J = 1.78, 8.07 Hz, 1H), 7.34 (m, 1H), 7.25 (m, 1H), 7.14 (m, 1H), 2.36 (s, 1H). 19 F NMR (470.54 MHz, CDCl 3 ): δ. -115.57 (s, 1F). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 160.5 (d, J = 249.28 Hz), 150.66 (d, J = 2.13 Hz), 150.15, 137.07, 132.11, 130.94 (d, J = 3.07 Hz), 130.16 (d, J = 8.51 Hz), 127.45 (d, J = 11.73 Hz), 124.55 (d, J = 3.58 Hz), 124.05 (d, J = 8.82 Hz), 116.21 (d, J = 23.02 Hz), 18.29. MS (m/z ESI, CH 3 OH) Calculated: 188.1 [M+H] + Found: 188.2 [M+H] +. 2-(2,4-difluorophenyl)-5-methylpyridine (2,4-dFmppy). Yield: 54%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.53 (s, 1H), 7.98 (td, J = 6.71, 8.85 Hz, 1H), 7.64 (dd, J = 2.17, 8.07 Hz 1H), 7.56 (dd, J = 1.92, 8.09 Hz, 1H), 6.98 (td, J = 2.39, 8.41 Hz, 1H), 6.89 (ddd, J = 2.50, 8.83, 11.28 Hz, 1H), 2.37 (s, 3H). 19 F NMR (470.54 MHz, CDCl 3 ): δ. -107.86 (d, J = 8.05 Hz, 1F), -111.12 (d, J = 8.37 Hz, 1F). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 164.14 (d, J = 11.97 Hz), 161.88 (dd, J = 12.00, 68.44 Hz), 159.60 (d, J = 11.92 Hz), 150.13, 149.79 (d, J = 2.42 Hz), 137.31, 132.26, 132.06 (d, J = 4.57, 9.61 Hz), 123.81 (d, J = 9.15 Hz), 111.94 (dd, J = 3.65, 21.03 Hz), 104.43 (dd, J = 25.43, 27.01), 18.31. MS (m/z ESI, CH 3 OH) Calculated: 206.1 [M+H] + Found: 206.2 [M+H] +. 2-(2,6-difluorophenyl)-5-methylpyridine (2,6-dFmppy). Yield: 49%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.58 (d, J = 1.94 Hz, 1H), 7.59 (dd, J = 1.78, 7.95 Hz, 1H), 7.38 (d, J = 7.91 Hz, 1H), 7.31 (tt, J = 6.30, 8.37 Hz, 1H), 6.98 (td, J =4.23, 8.1 Hz, 1H), 2.38 (s, 3H). 19 F NMR (470.54 MHz, CDCl 3 ): δ. -112.859 (s, 2F). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 160.58 (dd, J = 6.96, 250.21 Hz), 150.18, 146.49, 137.04, 132.79, 130.00 (t, J = 10.39 Hz), 125.49 (t, J = 1.48 Hz), 117.99 (t, J = 18.19 Hz), 111.84 (dd, J = 20.37, 5.91 Hz), 18.40. MS (m/z ESI, CH 3 OH) Calculated: 206.1 [M+H] + Found: 206.2 [M+H] +. S3

5-methyl-2-(2,4,6-trifluorophenyl)pyridine (2,4,6-tFmppy). Yield: 58%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.57 (s, 1H), 7.59 (m, 1H), 7.34 (d, J = 7.93 Hz, 1H), 6.76 (m, 2H), 2.39 (s, 1H). 19 F NMR (470.54 MHz, CDCl 3 ): δ. -105.529 (s, 1F), -109.55 (d, J = 6.61, 2F). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 162.55 (dt, J = 15.52, 15.52, 250.36 Hz), 162.04 (ddd, J = 9.66, 14.92, 251.44 Hz), 150.26, 145.72, 137.19, 133.00, 125.48, 114.60 (m), 100.74 (m), 18.41. MS (m/z ESI, CH 3 OH) Calculated: 224.1 [M+H] + Found: 224.3 [M+H] +. Synthesis of PFmppy and PFMeOppy. In a typical reaction, K 3 PO 4 (4.0 equiv), 1,10- phenanthroline (10 mol %), corresponding 2-bromopyridine (6.0 mmol), pentafluorobenzene (4.5 equiv), 1:1 DMF/Xylenes (20 ml) were degassed by four cycles of vacuum and argon, at which point CuI (10 mol %) was added. The solution was heated to 120 o C overnight. Once cooled, the reaction was poured into a separatory funnel containing diethyl ether and 1:1 water/nh 4 OH. The aqueous phase was extracted with diethyl ether, and the combined extracts were dried with Na 2 SO 4, and the solvents were removed in vacuo. The crude product was chromatographed on silica gel using 10% EtOAc/Hexanes as the eluent. 5-methyl-2-(perfluorophenyl)pyridine (PFmppy). Yield: 55%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.60 (s, 1H), 7.66 (dd, J = 2.06, 7.95 Hz, 1H), 7.38 (d, J = 7.93 Hz, 1H), 2.43 (s, 3H). 19 F NMR (470.54 MHz, CDCl 3 ): δ. -141.29 (dd, J = 7.93, 22.50 Hz, 2F), -152.21 (t, J = 20.23 Hz, 1F), - 160.08 (td, J = 7.48, 21.74 Hz, 2F). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 150.57, 144.78 (dm, J = 245.96 Hz), 143.74, 141.31 (dm, J = 254.87 Hz), 137.94 (dm, J = 253.04 Hz), 137.64, 134.12, 125.61, 115.24 (m), 18.51. MS (m/z ESI, CH 3 OH) Calculated: 260.0 [M+H] + Found: 260.3 [M+H] +. 5-methoxy-2-(perfluorophenyl)pyridine (PFMeOppy). Yield: 81%. 1 H NMR (500 MHz, CDCl 3 ): δ. 8.44 (d, J = 2.87 Hz, 1H), 7.41 (d, J = 8.60 Hz, 1H), 7.32 (dd, J = 2.96, 8.63 Hz, 1H), 3.92 (s, 3H). 19 F NMR (470.54 MHz, CDCl 3 ): δ. -141.53 (dd, J = 8.10, 22.68 Hz, 2F), -152.74 (t, J = 20.70 Hz, 1F), -160.32 (td, J = 6.88, 21.67 Hz, 2F). 13 C NMR (125.77 MHz, CDCl 3 ): δ. 155.89, 144.78 (dm, J = 249.59 Hz), 141.08 (dm, J = 254.51 Hz), 138.51, 138.14, 137.91 (dm, J = 252.96 Hz), 126.47, 121.02, 115.13 (m), 55.86. MS (m/z ESI, CH 3 OH) Calculated: 276.0 [M+H] + Found: 276.2 [M+H] +. S4

Figure S1. 1 H-NMR spectrum (500 MHz) of 2a in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. Figure S2. 19 F-NMR spectrum (470.54 MHz) of 2a in acetone-d 6. S5

Figure S3. 13 C-NMR spectrum (125.77 MHz) of 2a in acetone-d 6. Residual solvent signals at 29.8 and 206.2. Figure S4. 1 H-NMR spectrum (500 MHz) of 2b in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. S6

Figure S5. 19 F-NMR spectrum (470.54 MHz) of 2b in acetone-d 6. Figure S6. 13 C-NMR spectrum (125.77 MHz) of 2b in acetone-d 6. Residual solvent signals at 29.8 and 206.2. S7

Figure S7. 1 H-NMR spectrum (500 MHz) of 2c in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. Figure S8. 19 F-NMR spectrum (470.54 MHz) of 2c in acetone-d 6. S8

Figure S9. 13 C-NMR spectrum (125.77 MHz) of 2c in acetone-d 6. Residual solvent signals at 29.8 and 206.2. Figure S10. 1 H-NMR spectrum (500 MHz) of 2d in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. S9

Figure S11. 19 F-NMR spectrum (470.54 MHz) of 2d in acetone-d 6. Figure S12. 13 C-NMR spectrum (125.77 MHz) of 2d in acetone-d 6. Residual solvent signals at 29.8 and 206.2. S10

Figure S13. 1 H-NMR spectrum (500 MHz) of 2e in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. Figure S14. 19 F-NMR spectrum (470.54 MHz) of 2e in acetone-d 6. S11

Figure S15. 13 C-NMR spectrum (125.77 MHz) of 2e in acetone-d 6. Residual solvent signals at 29.8 and 206.2. Figure S16. 1 H-NMR spectrum (500 MHz) of 2f in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. S12

Figure S17. 19 F-NMR spectrum (470.54 MHz) of 2f in acetone-d 6. Figure S18. 13 C-NMR spectrum (125.77 MHz) of 2f in acetone-d 6. Residual solvent signals at 29.8 and 206.2. S13

Figure S19. 1 H-NMR spectrum (500 MHz) of 3a in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. Figure S20. 19 F-NMR spectrum (470.54 MHz) of 3a in acetone-d 6. Note: Trace unreacted ligand is present and was removed with subsequent recrystallization. S14

Figure S21. 13 C-NMR spectrum (125.77 MHz) of 3a in acetone-d 6. Residual solvent signals at 29.8 and 206.2. Figure S22. 1 H-NMR spectrum (500 MHz) of 3b in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. S15

Figure S23. 19 F-NMR spectrum (470.54 MHz) of 3b in acetone-d 6. Figure S24. 13 C-NMR spectrum (125.77 MHz) of 3b in acetone-d 6. Residual solvent signals at 29.8 and 206.2. S16

Figure S25. 1 H-NMR spectrum (500 MHz) of 3c in acetone-d 6. Residual solvent signals at 2.0 and 2.8 ppm. Figure S26. 19 F-NMR spectrum (470.54 MHz) of 3c in acetone-d 6. Note: trace unreacted ligand is present but was removed with subsequent recrystallization. S17

Figure S27. 13 C-NMR spectrum (125.77 MHz) of 3c in acetone-d 6. Residual solvent signals at 29.8 and 206.2. Figure S28. 19 F-NMR spectrum (282.37 MHz) of crude reaction of 1a with 2,4-dFmppy, showing the production of the C-F activation product (2b), C-H activation product (2d), and the byproducts of the generated HF with the borosilicate glass (BF 3 OH - and BF 4 - ). S18

Figure S29. 19 F-NMR spectrum (282.37 MHz) of crude reaction of 1a with 2-Fmppy, showing the production of the C-H activation product (2c) and the byproducts of the generated HF with the borosilicate glass (BF 3 OH - and BF 4 - ). Figure S30. 1 H-NMR spectrum (300.13 MHz) in DMSO-d 6 of the hydrazone generated from the oxidation products from crude reaction of 1a with 2-Fmppy reacting with 2,4- dinitrophenylhydrazine (DNPH) (red). The spectrum is overlayed with that of the pure hydrazone generated from the reaction of glyoxal with DNPH (blue). Unreacted DNPH indicated. S19

Figure S31. ESI-mass spectrum of the crude reaction of 1a with 2,4-dFmppy, showing both the C-F activation product (2b) and the C-H activation product (2d). Spectrum collected with a 50 µm methanol solution. Figure S32. ESI-mass spectrum of the crude reaction of 1a with 2-Fmppy, showing both the C-F activation product (2a) and the C-H activation product (2c). Spectrum collected with a 50 µm methanol solution. S20

Figure S33. UV-Vis absorption spectra of chloro complexes 2a (black), 2b (orange), 2c (cyan), 2d (green), 2e (yellow), and 2f (blue). All spectra were recorded at room temperature using 10 µm acetonitrile solutions. Figure S34. UV-Vis absorption spectra of cyano complexes 3a (orange), 3b (pink), and 3c (black dashed). All spectra were recorded at room temperature using 10 µm acetonitrile solutions. S21

Figure S35. Experimental (purple) and Calculated (black dashed) UV-Vis absorption spectra of 2c. Calculated spectra were determined from Gaussian 09 TD-DFT calculations using Gaussum software with a fwhm = 4000 cm -1. Oscillator strengths are included as vertical lines. Figure S36. Experimental (green) and Calculated (black dashed) UV-Vis absorption spectra of 2f. Calculated spectra were determined from Gaussian 09 TD-DFT calculations using Gaussum software with a fwhm = 4000 cm -1. Oscillator strengths are included as vertical lines. S22

Figure S37. Experimental (orange) and Calculated (black dashed) UV-Vis absorption spectra of 3c. Calculated spectra were determined from Gaussian 09 TD-DFT calculations using Gaussum software with a fwhm = 4000 cm -1. Oscillator strengths are included as vertical lines. Figure S38. Relationship between experimental emission energy and energy difference between the total energies of singlet and triplet excited states at the optimized triplet geometry. S23

Figure S39. Combined CO 2 evolution traces using 2b (solid), 3a (dashed), and [Ir(dF(CF 3 )ppy) 2 (dtbbpy)]pf 6 (dot-dashed). 1-naphthalene acetic acid (blue), 4-biphenylacetic acid (gold), diphenylacetic acid (black), cyclohexylcarboxylic acid (green), 3,3,3- triphenylpropionic acid (pink). Figure S40. CO 2 evolution traces using 2b with diphenylacetic acid at varying catalyst concentrations. 0.1 mol % (black), 0.05 mol % (orange), 0.025 mol % (blue), 0.0125 mol % (green), 0.010 mol % (yellow). S24

Figure S41. Triplet frontier orbital diagrams of 3a-3c. Increasing fluorination leads to a decrease in metal character in the triplet state, most notably in the LSOMOs. S25

-3 LUMO+6-4 LUMO+2-5 LUMO+5 LUMO Energy (ev) -6-7 LUMO+1 E = 3.08 ev -8 HOMO-1 HOMO -9 HOMO-4-10 HOMO-3 Figure S42. Expanded Frontier Orbital diagram of 2c. HOMO-6 S26

-3 LUMO+6-4 LUMO+2-5 LUMO+5 LUMO Energy (ev) -6-7 LUMO+1 E = 3.52 ev -8 HOMO-1 HOMO -9 HOMO-3-10 HOMO-2 Figure S43. Expanded Frontier Orbital Diagram of 3c. HOMO-4 S27

DFT Results for 2a SCF Energy: -1851.6799011 a.u. Frontier Orbitals HOMO -8.009 ev LUMO -5.007 ev S28

Singlet Optimized Coordinates for 2a: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.257272 3.241977-0.121406 2 6 0-3.730488 1.251673-0.140774 3 6 0-2.386080 0.873981-0.177633 4 6 0-1.222972 1.843854-0.164555 5 6 0-0.022948 3.969804-0.051954 6 6 0 1.214244 3.239377-0.030216 7 7 0-0.024334 1.254940-0.112694 8 6 0 1.176732 1.840550-0.066772 9 6 0-4.735788 0.252535-0.092153 10 6 0-4.330904-1.106987-0.079005 11 6 0-2.975287-1.444269-0.111926 12 7 0-2.049792-0.459023-0.167400 13 6 0 2.340528 0.877425-0.174327 14 6 0 3.683654 1.259861-0.195118 15 6 0 4.693327 0.273226-0.293138 16 7 0 2.008505-0.453326-0.263714 17 6 0 2.942458-1.432759-0.321580 18 6 0 4.297503-1.089800-0.344268 19 77 0-0.022291-0.697246-0.225538 20 17 0-0.239884-0.422704-2.579709 21 7 0 0.007867-2.756099-0.322642 22 6 0 0.346684-3.349898 0.862649 23 6 0 0.437730-4.746983 0.941735 24 6 0 0.163707-5.512017-0.193165 25 6 0-0.237691-4.885994-1.382352 26 6 0-0.332477-3.488188-1.419673 27 1 0 0.686855-5.247153 1.865885 28 6 0 0.189888-1.095992 1.792762 29 6 0 0.158614-0.146909 2.813059 30 6 0 0.363285-0.563120 4.133387 31 6 0 0.601695-1.917217 4.416636 32 6 0 0.633351-2.864030 3.381398 33 6 0 0.429082-2.446542 2.055300 34 1 0-0.017347 0.896004 2.589557 35 1 0 0.338594 0.160737 4.937615 36 6 0-0.059906 5.512562-0.017865 37 6 0 1.347626 6.154549 0.036230 38 1 0 1.895007 5.837903 0.950303 39 1 0 1.274158 7.263702 0.059083 40 1 0 1.944370 5.879885-0.860577 41 6 0-0.835767 5.978741 1.232486 42 1 0-0.335791 5.613789 2.155809 43 1 0-1.879948 5.603038 1.232021 44 1 0-0.881586 7.088633 1.276301 45 6 0-0.763110 6.037011-1.288773 46 1 0-0.212964 5.710765-2.197913 47 1 0-0.805179 7.147831-1.286116 48 1 0-1.806679 5.667303-1.364345 49 6 0-6.239710 0.600925-0.039976 50 6 0-6.858412 0.015766 1.248538 51 1 0-6.758343-1.088610 1.288818 52 1 0-7.943189 0.251643 1.307322 53 1 0-6.359714 0.442278 2.145783 54 6 0-6.513067 2.125039-0.037327 55 1 0-6.051733 2.609640 0.850596 56 1 0-7.605126 2.329782 0.002636 57 1 0-6.118478 2.602652-0.960098 58 6 0-6.947727 0.000218-1.272730 59 1 0-6.844020-1.104111-1.307612 60 1 0-6.517023 0.419667-2.207728 61 1 0-8.034704 0.232799-1.254718 62 6 0 6.175032 0.705969-0.347994 63 6 0 6.534931 1.494645 0.929369 64 1 0 5.911917 2.406278 1.039500 65 1 0 7.597150 1.821920 0.902500 66 1 0 6.387166 0.860949 1.830188 67 6 0 7.154348-0.487719-0.455445 68 1 0 7.064431-1.156287 0.427756 69 1 0 8.206603-0.131023-0.498757 70 1 0 6.964975-1.075618-1.379708 71 6 0 6.395346 1.602012-1.587138 72 1 0 5.765807 2.515393-1.552160 73 1 0 6.144955 1.045256-2.516373 74 1 0 7.454825 1.931638-1.653767 75 1 0 0.799197-3.902891 3.625291 76 1 0 2.169259 3.737353-0.008684 77 1 0-5.060760-1.903631-0.038688 78 1 0-2.671854-2.481063-0.097611 79 6 0-0.557609-5.692112-2.606092 80 1 0 0.753355-2.233870 5.440502 81 1 0-0.433291-6.780643-2.422674 82 1 0 0.124426-5.397655-3.431880 83 1 0-1.606452-5.503388-2.916293 84 1 0 2.648428-2.470312-0.371478 85 1 0 5.017857-1.890592-0.410580 86 1 0-2.205811 3.757286-0.135560 87 1 0-3.975607 2.300678-0.137380 88 1 0 3.942109 2.306608-0.142258 89 1 0 0.233661-6.591267-0.137048 90 1 0-0.636050-3.001865-2.331965 S29

DFT Results for 2b SCF Energy: -1950.9243955 a.u. Frontier Orbitals HOMO -8.176 ev LUMO -5.098 ev S30

Singlet Optimized Coordinates for 2b: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.265797 3.234681-0.244941 2 6 0-3.744070 1.247187-0.218496 3 6 0-2.399738 0.868027-0.261266 4 6 0-1.234301 1.836290-0.279429 5 6 0-0.029375 3.960820-0.192217 6 6 0 1.207224 3.228467-0.183409 7 7 0-0.035473 1.246057-0.240250 8 6 0 1.167102 1.829516-0.212812 9 6 0-4.749369 0.248979-0.143403 10 6 0-4.344607-1.109927-0.106308 11 6 0-2.989976-1.448324-0.146559 12 7 0-2.064784-0.464959-0.230695 13 6 0 2.327395 0.862194-0.326768 14 6 0 3.671960 1.239636-0.362928 15 6 0 4.677224 0.247983-0.462175 16 7 0 1.990384-0.468335-0.401585 17 6 0 2.920357-1.451128-0.464296 18 6 0 4.275734-1.113473-0.502992 19 77 0-0.039609-0.707476-0.322631 20 17 0-0.319932-0.476967-2.674903 21 7 0-0.014364-2.767321-0.387603 22 6 0 0.368316-3.340427 0.794713 23 6 0 0.460669-4.735797 0.895846 24 6 0 0.137167-5.520932-0.211902 25 6 0-0.314314-4.915951-1.394128 26 6 0-0.404039-3.518560-1.454859 27 1 0 0.744443-5.219434 1.818822 28 6 0 0.228143-1.072512 1.694149 29 6 0 0.226273-0.106533 2.698777 30 6 0 0.483344-0.498543 4.017529 31 6 0 0.744320-1.846194 4.313518 32 6 0 0.744941-2.810137 3.293503 33 6 0 0.488288-2.416702 1.969310 34 1 0 0.036233 0.931322 2.463137 35 9 0 0.483791 0.425092 5.009949 36 6 0-0.063896 5.503684-0.155994 37 6 0 1.344870 6.143504-0.109688 38 1 0 1.897604 5.823104 0.799953 39 1 0 1.273114 7.252688-0.082511 40 1 0 1.935434 5.870933-1.011065 41 6 0-0.829868 5.968846 1.101285 42 1 0-0.324568 5.600405 2.020331 43 1 0-1.875124 5.596223 1.107692 44 1 0-0.872936 7.078716 1.148339 45 6 0-0.775822 6.031576-1.420203 46 1 0-0.232153 5.707582-2.333973 47 1 0-0.817117 7.142469-1.414137 48 1 0-1.819979 5.662124-1.488841 49 6 0-6.253358 0.596896-0.090885 50 6 0-6.864283 0.042174 1.214488 51 1 0-6.761497-1.060710 1.280998 52 1 0-7.949253 0.277299 1.272856 53 1 0-6.361930 0.491511 2.098393 54 6 0-6.528508 2.120083-0.124936 55 1 0-6.063748 2.627464 0.748187 56 1 0-7.620722 2.324260-0.085335 57 1 0-6.138689 2.574418-1.061452 58 6 0-6.967671-0.034668-1.304997 59 1 0-6.863790-1.139516-1.313566 60 1 0-6.542447 0.361496-2.252587 61 1 0-8.054788 0.197134-1.287039 62 6 0 6.160888 0.672616-0.525356 63 6 0 6.529431 1.461208 0.749585 64 1 0 5.911472 2.376178 0.860536 65 1 0 7.593423 1.782258 0.719219 66 1 0 6.380902 0.829447 1.651764 67 6 0 7.133438-0.526797-0.633510 68 1 0 7.043445-1.192798 0.251708 69 1 0 8.187505-0.176253-0.681439 70 1 0 6.937222-1.116026-1.555506 71 6 0 6.381821 1.564861-1.766759 72 1 0 5.757806 2.481926-1.730910 73 1 0 6.125155 1.007763-2.694000 74 1 0 7.443063 1.888091-1.837286 75 1 0 0.929607-3.843250 3.547845 76 1 0 2.163352 3.724859-0.174109 77 1 0 3.934840 2.285734-0.318098 78 1 0-5.074069-1.905575-0.044944 79 1 0-2.687322-2.484877-0.117793 80 6 0-0.696056-5.744309-2.584748 81 1 0 0.938336-2.145231 5.335554 82 1 0-0.569874-6.829742-2.384939 83 1 0-0.053699-5.470868-3.448463 84 1 0-1.757984-5.555270-2.847165 85 1 0 0.204739-6.599225-0.137726 86 1 0-0.746707-3.047992-2.361753 87 1 0-3.989222 2.296167-0.233901 88 1 0-2.213780 3.751302-0.247172 89 1 0 2.622788-2.488004-0.502722 90 1 0 4.992053-1.917763-0.570053 S31

DFT Results for 2c SCF Energy: -1950.9239826 a.u. Frontier Orbitals HOMO -8.175 ev LUMO -5.096 ev S32

Singlet Optimized Coordinaes for 2c: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.378906 3.285800-0.004303 2 6 0-3.791258 1.222845-0.102638 3 6 0-2.436151 0.889969-0.173619 4 6 0-1.302688 1.893755-0.124401 5 6 0-0.166461 4.046693 0.092705 6 6 0 1.092680 3.354890 0.060143 7 7 0-0.085896 1.340458-0.118735 8 6 0 1.097312 1.959591-0.053779 9 6 0-4.764515 0.191045-0.093712 10 6 0-4.317565-1.153856-0.153205 11 6 0-2.952966-1.446111-0.218464 12 7 0-2.059126-0.430750-0.234808 13 6 0 2.288220 1.039700-0.226171 14 6 0 3.619278 1.463139-0.237013 15 6 0 4.656819 0.514095-0.397258 16 7 0 1.995106-0.293848-0.385305 17 6 0 2.957215-1.239574-0.506773 18 6 0 4.300956-0.855073-0.522298 19 77 0-0.026622-0.602625-0.332668 20 17 0-0.296802-0.212448-2.665428 21 7 0 0.063695-2.650142-0.537164 22 6 0 0.451768-3.298666 0.606115 23 6 0 0.589134-4.697577 0.591152 24 6 0 0.305699-5.400440-0.580478 25 6 0-0.150000-4.719670-1.716234 26 6 0-0.286062-3.327392-1.666390 27 1 0 0.878501-5.258207 1.461780 28 6 0 0.235846-1.097015 1.655809 29 6 0 0.191093-0.190444 2.712931 30 6 0 0.440852-0.645142 4.009289 31 6 0 0.738441-1.995459 4.235187 32 6 0 0.784248-2.905899 3.167731 33 6 0 0.532094-2.451526 1.852616 34 1 0-0.028127 0.852754 2.534302 35 1 0 0.407178 0.047267 4.840462 36 6 0-0.250022 5.583296 0.215681 37 6 0 1.137761 6.264404 0.295620 38 1 0 1.703305 5.912457 1.185433 39 1 0 1.030731 7.367576 0.383642 40 1 0 1.733932 6.060881-0.620270 41 6 0-1.027234 5.953214 1.497188 42 1 0-0.507672 5.551411 2.393996 43 1 0-2.059774 5.546847 1.483625 44 1 0-1.105949 7.056871 1.605261 45 6 0-0.981557 6.157787-1.016887 46 1 0-0.430552 5.902026-1.947783 47 1 0-1.057704 7.264792-0.949495 48 1 0-2.013880 5.760344-1.105117 49 6 0-6.277943 0.487850-0.008596 50 6 0-6.861845-0.178825 1.256315 51 1 0-6.725854-1.280009 1.241652 52 1 0-7.952830 0.018375 1.338040 53 1 0-6.366133 0.219814 2.167899 54 6 0-6.599439 2.000346 0.070999 55 1 0-6.143173 2.456255 0.976504 56 1 0-7.696931 2.167413 0.132166 57 1 0-6.231234 2.534241-0.831616 58 6 0-6.981778-0.075163-1.261567 59 1 0-6.843777-1.172609-1.351430 60 1 0-6.576242 0.402529-2.179727 61 1 0-8.075297 0.120927-1.220538 62 6 0 6.124983 0.992517-0.435159 63 6 0 6.470239 1.715133 0.884661 64 1 0 5.821895 2.600172 1.051135 65 1 0 7.522485 2.073932 0.872448 66 1 0 6.346277 1.025628 1.747347 67 6 0 7.137597-0.163919-0.616764 68 1 0 7.072878-0.885040 0.226426 69 1 0 8.178874 0.225040-0.644210 70 1 0 6.959032-0.702401-1.572739 71 6 0 6.311544 1.965467-1.620521 72 1 0 5.656506 2.856687-1.528778 73 1 0 6.071381 1.457094-2.579642 74 1 0 7.360788 2.328863-1.672384 75 9 0 1.054440-4.203316 3.440816 76 1 0 2.032327 3.880324 0.099592 77 1 0-5.021722-1.974241-0.145172 78 1 0-2.617789-2.472229-0.260399 79 6 0-0.484468-5.462507-2.975786 80 1 0 0.926646-2.339859 5.244072 81 1 0-0.323275-6.555641-2.860824 82 1 0 0.161848-5.099754-3.802962 83 1 0-1.547915-5.288957-3.242277 84 1 0 2.693958-2.281282-0.610848 85 1 0 5.043910-1.629036-0.638711 86 1 0-2.342832 3.771318 0.021406 87 1 0-4.068853 2.262111-0.043730 88 1 0 3.847164 2.512597-0.127172 89 1 0 0.410208-6.478405-0.592182 90 1 0-0.630704-2.798960-2.539491 S33

DFT Results for 2d SCF Energy: -2050.1666685 a.u. Frontier Orbitals HOMO -8.337 ev LUMO -5.184 ev S34

Singlet Optimized Coordinates for 2d --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.394728 3.271311-0.047789 2 6 0-3.783889 1.275802-0.210139 3 6 0-2.411619 0.902581-0.240959 4 6 0-1.317739 1.848861-0.175019 5 6 0-0.177988 4.021950 0.024591 6 6 0 1.053742 3.369410-0.027549 7 7 0-0.097879 1.248020-0.224669 8 6 0 1.094941 1.922470-0.176489 9 6 0-4.804569 0.319293-0.245639 10 6 0-4.412850-1.049888-0.320979 11 6 0-3.047590-1.376818-0.375409 12 7 0-2.071130-0.452599-0.342609 13 6 0 2.234861 1.088369-0.340689 14 6 0 3.585661 1.556099-0.376229 15 6 0 4.663591 0.688278-0.562659 16 7 0 1.995310-0.293871-0.527699 17 6 0 3.032320-1.128871-0.707029 18 6 0 4.371130-0.704982-0.724149 19 77 0-0.022820-0.721300-0.429039 20 17 0-0.222820-0.438380-2.939519 21 7 0 0.082059-2.796400-0.523459 22 6 0 0.382979-3.435640 0.687261 23 6 0 0.534198-4.845690 0.694741 24 6 0 0.339328-5.586860-0.476349 25 6 0-0.019372-4.928480-1.689479 26 6 0-0.130821-3.533420-1.648289 27 1 0 0.792418-5.341050 1.621521 28 6 0 0.186420-1.139520 1.532571 29 6 0 0.153830-0.202050 2.586711 30 6 0 0.383510-0.639290 3.897731 31 6 0 0.654799-1.974910 4.224561 32 6 0 0.678799-2.885850 3.172861 33 6 0 0.443139-2.530690 1.820831 34 1 0-0.031449 0.850050 2.394031 35 9 0 0.359221 0.293900 4.954871 36 6 0-0.278627 5.560300 0.172311 37 6 0 1.102113 6.260420 0.244201 38 1 0 1.684423 5.910900 1.104311 39 1 0 0.960744 7.344600 0.348231 40 1 0 1.689563 6.082040-0.663729 41 6 0-1.055857 5.902711 1.477511 42 1 0-0.533187 5.499531 2.352731 43 1 0-2.063447 5.474371 1.467261 44 1 0-1.145686 6.992341 1.596471 45 6 0-1.047137 6.146661-1.048069 46 1 0-0.520017 5.914571-1.980629 47 1 0-1.133406 7.239491-0.958159 48 1 0-2.055417 5.727741-1.125719 49 6 0-6.303579 0.679743-0.206919 50 6 0-6.962420 0.003393 1.031611 51 1 0-6.860350-1.086817 0.998801 52 1 0-8.033500 0.243474 1.070881 53 1 0-6.494929 0.353503 1.959161 54 6 0-6.547319 2.206793-0.112859 55 1 0-6.106028 2.630993 0.796371 56 1 0-7.625999 2.405724-0.086959 57 1 0-6.129108 2.736723-0.976399 58 6 0-6.988410 0.155403-1.503499 59 1 0-6.882060-0.930207-1.604249 60 1 0-6.541429 0.617383-2.391359 61 1 0-8.060949 0.393074-1.491269 62 6 0 6.107661 1.241258-0.596049 63 6 0 6.422531 1.960757 0.748021 64 1 0 5.732812 2.792148 0.927291 65 1 0 7.446181 2.362107 0.739131 66 1 0 6.330301 1.265337 1.590371 67 6 0 7.162460 0.124207-0.802729 68 1 0 7.132550-0.613843 0.007301 69 1 0 8.167451 0.565717-0.819539 70 1 0 7.010410-0.403253-1.751479 71 6 0 6.244861 2.259307-1.766369 72 1 0 5.551762 3.098998-1.648929 73 1 0 6.022001 1.777658-2.725449 74 1 0 7.267282 2.662117-1.807929 75 9 0 0.955428-4.227480 3.520521 76 1 0 1.983582 3.916919 0.030551 77 1 0 3.751732 2.621649-0.254269 78 6 0-0.253112-5.685220-2.984519 79 1 0 0.838029-2.287460 5.248141 80 1 0-0.120453-6.762890-2.834069 81 1 0 0.446278-5.368190-3.769039 82 1 0-1.267332-5.524259-3.373289 83 1 0-4.013099 2.331912-0.153859 84 1 0-2.361288 3.758241 0.000321 85 1 0-5.144180-1.851817-0.342029 86 1 0-2.719311-2.408268-0.445799 87 1 0 2.778229-2.175991-0.836829 88 1 0 5.147980-1.446692-0.860959 89 1 0 0.457327-6.669020-0.459479 90 1 0-0.365221-2.944080-2.530989 S35

DFT Results for 2e SCF Energy: -2248.6254977 a.u. Frontier Orbitals HOMO -8.559 ev LUMO -5.199 ev S36

Singlet Optimized Coordinates for 2e --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.512463 3.271347-0.086462 2 6 0-3.869200 1.143427-0.179266 3 6 0-2.508061 0.853266-0.305741 4 6 0-1.402229 1.888236-0.268130 5 6 0-0.318595 4.062305 0.004059 6 6 0 0.957570 3.409889-0.103662 7 7 0-0.170682 1.371222-0.328705 8 6 0 0.996893 2.021380-0.278894 9 6 0-4.811318 0.082790-0.166810 10 6 0-4.327427-1.246094-0.273846 11 6 0-2.958403-1.495368-0.393770 12 7 0-2.095667-0.453574-0.416342 13 6 0 2.206057 1.141804-0.523028 14 6 0 3.525107 1.601177-0.552276 15 6 0 4.582258 0.686806-0.775521 16 7 0 1.943680-0.193037-0.723131 17 6 0 2.926485-1.106324-0.909192 18 6 0 4.258382-0.685132-0.946930 19 77 0-0.064826-0.562851-0.600264 20 17 0-0.458203-0.120744-2.905962 21 7 0 0.068875-2.602255-0.871790 22 6 0 0.546768-3.270922 0.224364 23 6 0 0.722294-4.664988 0.155795 24 6 0 0.380223-5.344135-1.016864 25 6 0-0.170997-4.645782-2.099840 26 6 0-0.337999-3.258530-1.996863 27 1 0 1.082424-5.240913 0.989215 28 6 0 0.312060-1.109094 1.364784 29 6 0 0.294440-0.244916 2.464968 30 6 0 0.644001-0.734785 3.723713 31 6 0 1.012526-2.076422 3.878602 32 6 0 1.026657-2.945589 2.775208 33 6 0 0.673848-2.458164 1.494302 34 9 0-0.047598 1.056994 2.328225 35 9 0 0.631545 0.093706 4.798033 36 6 0-0.440371 5.588074 0.206185 37 6 0 0.929968 6.304438 0.278924 38 1 0 1.531906 5.925800 1.133349 39 1 0 0.795370 7.398412 0.425272 40 1 0 1.503235 6.163562-0.662817 41 6 0-1.186344 5.873353 1.527953 42 1 0-0.628327 5.443953 2.388160 43 1 0-2.207749 5.439648 1.526444 44 1 0-1.291358 6.967873 1.692686 45 6 0-1.226262 6.199646-0.973301 46 1 0-0.697676 6.005350-1.931598 47 1 0-1.331329 7.299290-0.849016 48 1 0-2.249015 5.775748-1.049359 49 6 0-6.329863 0.331176-0.032640 50 6 0-6.859143-0.379348 1.232241 51 1 0-6.689831-1.475203 1.190246 52 1 0-7.953231-0.217960 1.345866 53 1 0-6.352316 0.015862 2.139116 54 6 0-6.694269 1.831107 0.086870 55 1 0-6.228369 2.282653 0.989524 56 1 0-7.794364 1.963215 0.179098 57 1 0-6.365921 2.393633-0.813813 58 6 0-7.050320-0.227143-1.278637 59 1 0-6.882795-1.317943-1.395563 60 1 0-6.683463 0.280733-2.196905 61 1 0-8.147650-0.065111-1.205330 62 6 0 6.037031 1.203421-0.825682 63 6 0 6.395973 1.873233 0.518256 64 1 0 5.730189 2.732690 0.740588 65 1 0 7.438811 2.258308 0.499397 66 1 0 6.309322 1.141719 1.350506 67 6 0 7.072612 0.082008-1.082769 68 1 0 7.046218-0.677540-0.271793 69 1 0 8.103317 0.497614-1.116745 70 1 0 6.883416-0.417626-2.057620 71 6 0 6.172141 2.233522-1.968611 72 1 0 5.498961 3.103334-1.820418 73 1 0 5.920918 1.763645-2.944297 74 1 0 7.211034 2.624560-2.027270 75 9 0 1.367965-4.238471 2.981361 76 1 0 1.883273 3.960041-0.069994 77 1 0 3.728928 2.651117-0.405048 78 1 0-5.006479-2.087339-0.263583 79 1 0-2.595763-2.509627-0.474052 80 6 0-0.577480-5.362555-3.359438 81 9 0 1.347294-2.540955 5.108260 82 1 0-0.385486-6.455499-3.296440 83 1 0-0.005365-4.961105-4.223068 84 1 0-1.661268-5.210897-3.548815 85 1 0 0.512495-6.418400-1.066103 86 1 0-0.755684-2.715987-2.828497 87 1 0-4.174973 2.172092-0.084237 88 1 0-2.487794 3.726428-0.002004 89 1 0 2.688325-2.150513-1.043015 90 1 0 5.017507-1.434086-1.111870 S37

DFT Results for 2f SCF Energy: -2323.8190665 a.u. Frontier Orbitals HOMO -8.463 ev LUMO -5.157 ev S38

Singlet Optimized Coordinates for 2f --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.392104 3.423143-0.309479 2 6 0-3.820608 1.373606-0.214570 3 6 0-2.469484 1.031460-0.316251 4 6 0-1.329003 2.028978-0.369558 5 6 0-0.170987 4.176814-0.291244 6 6 0 1.082984 3.476173-0.347962 7 7 0-0.114674 1.469786-0.387108 8 6 0 1.074948 2.079647-0.400986 9 6 0-4.796044 0.347854-0.110037 10 6 0-4.354890-0.999824-0.104614 11 6 0-2.994544-1.300675-0.202539 12 7 0-2.099426-0.291216-0.313482 13 6 0 2.252491 1.140774-0.575633 14 6 0 3.586371 1.546746-0.653172 15 6 0 4.608215 0.577923-0.803487 16 7 0 1.942345-0.194613-0.657452 17 6 0 2.889165-1.157111-0.772829 18 6 0 4.234459-0.790726-0.856196 19 77 0-0.074716-0.475615-0.494256 20 17 0-0.469752-0.203975-2.827862 21 7 0-0.012501-2.519865-0.593559 22 6 0 0.452143-3.118562 0.546081 23 6 0 0.576276-4.515872 0.583552 24 6 0 0.196638-5.262307-0.530857 25 6 0-0.343443-4.619859-1.662398 26 6 0-0.455202-3.234961-1.658809 27 1 0 0.922418-5.043797 1.453747 28 6 0 0.297918-0.874913 1.509109 29 6 0 0.316086 0.070995 2.537616 30 6 0 0.658565-0.332413 3.829776 31 6 0 0.984339-1.670105 4.087007 32 6 0 0.962265-2.620311 3.054987 33 6 0 0.616923-2.219309 1.743977 34 9 0 0.015420 1.368268 2.299027 35 9 0 0.680782 0.575643 4.836719 36 6 0-0.240563 5.714559-0.217192 37 6 0 1.153832 6.385668-0.208714 38 1 0 1.747685 6.056137 0.671564 39 1 0 1.058047 7.491460-0.151716 40 1 0 1.715421 6.147237-1.137894 41 6 0-0.967572 6.129823 1.080195 42 1 0-0.418221 5.751393 1.969636 43 1 0-2.002588 5.731192 1.118375 44 1 0-1.035126 7.236512 1.156397 45 6 0-1.013616 6.251287-1.440286 46 1 0-0.498223 5.959640-2.381016 47 1 0-1.081171 7.360033-1.407028 48 1 0-2.050252 5.856710-1.476856 49 6 0-6.305325 0.654870 0.007519 50 6 0-6.848604 0.070460 1.329922 51 1 0-6.715945-1.030206 1.379170 52 1 0-7.935895 0.277303 1.434834 53 1 0-6.322329 0.522652 2.198283 54 6 0-6.619643 2.170571 0.002629 55 1 0-6.132109 2.679733 0.862227 56 1 0-7.713932 2.346698 0.088798 57 1 0-6.279390 2.644394-0.943499 58 6 0-7.052722 0.017982-1.183776 59 1 0-6.922351-1.083846-1.208954 60 1 0-6.676443 0.434361-2.143263 61 1 0-8.143641 0.222360-1.119184 62 6 0 6.079524 1.034828-0.902873 63 6 0 6.468709 1.800085 0.380132 64 1 0 5.833662 2.697184 0.532720 65 1 0 7.523809 2.145892 0.327070 66 1 0 6.360874 1.142848 1.270040 67 6 0 7.073585-0.140278-1.068610 68 1 0 7.025536-0.828535-0.197198 69 1 0 8.117897 0.234735-1.139656 70 1 0 6.861783-0.712365-1.997909 71 6 0 6.243405 1.960760-2.127924 72 1 0 5.601467 2.862711-2.050709 73 1 0 5.970380 1.420365-3.060295 74 1 0 7.294748 2.309077-2.221544 75 9 0 1.261484-3.905032 3.357351 76 1 0 2.027266 3.993943-0.367034 77 1 0 3.828406 2.597004-0.598181 78 1 0-5.060360-1.815577-0.023565 79 1 0-2.665338-2.329573-0.198156 80 8 0-0.757953-5.297036-2.760850 81 9 0 1.312273-2.051145 5.346702 82 1 0 0.291793-6.338232-0.491141 83 1 0-0.862609-2.740529-2.523417 84 1 0-4.093204 2.415512-0.208330 85 1 0-2.351755 3.915169-0.262456 86 1 0 2.612552-2.199680-0.817940 87 1 0 4.964578-1.578596-0.963022 88 6 0-0.697840-6.663429-2.899102 89 1 0-1.096052-6.941759-3.894486 90 1 0-1.316395-7.146202-2.113074 91 1 0 0.357773-7.001537-2.824611 S39

DFT Results for 3a SCF Energy: -2028.7584652 a.u. Frontier Orbitals HOMO -8.416 ev LUMO -5.142 ev S40

Singlet Optimized Coordinates for 3a --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.171033 3.221686-0.134911 2 6 0-3.655366 1.322475-0.250326 3 6 0-2.330361 0.887813-0.239106 4 6 0-1.154279 1.820933-0.159540 5 6 0 0.066939 3.936731-0.158794 6 6 0 1.289489 3.193100-0.222059 7 7 0 0.032693 1.213111-0.212948 8 6 0 1.233866 1.793770-0.269187 9 6 0-4.702785 0.381951-0.330724 10 6 0-4.357453-0.995617-0.379015 11 6 0-3.008709-1.397593-0.363312 12 7 0-2.034336-0.454292-0.315437 13 6 0 2.384219 0.825913-0.314722 14 6 0 3.720501 1.218902-0.293942 15 6 0 4.740407 0.249007-0.304624 16 7 0 2.052064-0.509246-0.332550 17 6 0 2.997890-1.481920-0.329021 18 6 0 4.358495-1.122125-0.323697 19 77 0 0.007026-0.748887-0.336720 20 6 0 0.051723-0.521144-2.405949 21 7 0-0.040133-2.818704-0.447643 22 6 0-0.142351-3.427045 0.775546 23 6 0-0.165326-4.829993 0.858858 24 6 0-0.112051-5.586628-0.310041 25 6 0-0.009610-4.950080-1.552727 26 6 0 0.060682-3.547012-1.599836 27 6 0-0.048088-1.163592 1.706978 28 6 0-0.019175-0.219889 2.740838 29 6 0-0.048952-0.663030 4.077498 30 6 0-0.099628-2.039950 4.354316 31 6 0-0.138165-2.974052 3.309859 32 6 0-0.123619-2.531808 1.976763 33 1 0 0.026514 0.834218 2.507305 34 9 0-0.023390 0.230943 5.104041 35 6 0 0.048004 5.480599-0.141185 36 6 0 1.463521 6.106984-0.129471 37 1 0 2.027510 5.791919 0.775362 38 1 0 1.402996 7.217036-0.116413 39 1 0 2.037000 5.818198-1.036561 40 6 0-0.692864 5.978553 1.118891 41 1 0-0.179115 5.623673 2.038003 42 1 0-1.742888 5.620795 1.147529 43 1 0-0.724651 7.089638 1.141981 44 6 0-0.679556 5.991776-1.403259 45 1 0-0.151527 5.646339-2.318839 46 1 0-0.709951 7.102882-1.418621 47 1 0-1.726979 5.628141-1.450202 48 6 0-6.187085 0.825063-0.366920 49 6 0-6.933129 0.221890 0.839572 50 1 0-6.896338-0.886521 0.829081 51 1 0-8.003776 0.522696 0.829545 52 1 0-6.480928 0.580100 1.789739 53 6 0-6.374855 2.365047-0.305192 54 1 0-5.955369 2.783267 0.635566 55 1 0-7.453314 2.635439-0.332517 56 1 0-5.889980 2.864175-1.172687 57 6 0-6.839687 0.338342-1.678008 58 1 0-6.800215-0.766224-1.769640 59 1 0-6.321617 0.781879-2.556236 60 1 0-7.909440 0.640718-1.720651 61 6 0 6.214631 0.719350-0.295449 62 6 0 6.499546 1.534047 0.988206 63 1 0 5.850995 2.432003 1.061993 64 1 0 7.553477 1.889993 1.002532 65 1 0 6.332697 0.910456 1.892548 66 6 0 7.222139-0.450549-0.343093 67 1 0 7.107950-1.108993 0.544343 68 1 0 8.266677-0.068003-0.344279 69 1 0 7.084106-1.051272-1.267473 70 6 0 6.475677 1.615305-1.528694 71 1 0 5.831976 2.519856-1.526792 72 1 0 6.278568 1.053381-2.466417 73 1 0 7.529557 1.968729-1.545702 74 1 0-0.171433-4.026221 3.550898 75 1 0 2.247748 3.682653-0.242125 76 1 0-5.126722-1.753317-0.437744 77 1 0-2.753093-2.446486-0.415172 78 6 0 0.003124-5.754666-2.820562 79 1 0-0.109271-2.391596 5.378251 80 1 0-0.058075-6.845765-2.614646 81 1 0 0.928470-5.552544-3.396318 82 1 0-0.879840-5.476779-3.435995 83 1 0 0.141564-3.057413-2.556671 84 1 0 2.709998-2.523960-0.340746 85 1 0 5.093991-1.912331-0.331320 86 7 0 0.076033-0.403318-3.556815 87 1 0-0.147028-6.668358-0.245932 88 1 0-0.218160-5.343473 1.806960 89 1 0-3.854377 2.378668-0.204512 90 1 0-2.110222 3.751670-0.117846 91 1 0 3.967475 2.268388-0.264524 S41

DFT Results for 3b SCF Energy: -2128.0005569 a.u. Frontier Orbitals HOMO -8.629 ev LUMO -5.232 ev S42

Singlet Optimized Coordinates for 3b --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.263902 3.218789-0.089102 2 6 0-3.725752 1.359983-0.207665 3 6 0-2.396094 0.942170-0.263647 4 6 0-1.233158 1.885659-0.208511 5 6 0 0.040473 3.966742-0.024107 6 6 0 1.214046 3.246209-0.108808 7 7 0 0.007438 1.246085-0.266585 8 6 0 1.164305 1.769023-0.260727 9 6 0-4.763855 0.410006-0.242807 10 6 0-4.404358-0.962466-0.320145 11 6 0-3.049803-1.348140-0.372257 12 7 0-2.082711-0.394938-0.354499 13 6 0 2.197788 0.906752-0.404705 14 6 0 3.589538 1.388780-0.414788 15 6 0 4.609054 0.496677-0.564762 16 7 0 1.947928-0.351457-0.534546 17 6 0 2.961239-1.336955-0.686324 18 6 0 4.251500-0.959422-0.708329 19 77 0-0.033234-0.685738-0.475224 20 6 0-0.225910-0.443348-2.533362 21 7 0-0.045943-2.752363-0.579186 22 6 0 0.206532-3.362316 0.623607 23 6 0 0.285807-4.766143 0.683185 24 6 0 0.081688-5.515363-0.472433 25 6 0-0.218780-4.876791-1.679839 26 6 0-0.281629-3.474399-1.714253 27 1 0 0.487500-5.297430 1.595238 28 6 0 0.165454-1.092839 1.550761 29 6 0 0.212695-0.134890 2.563805 30 6 0 0.403738-0.547269 3.885308 31 6 0 0.561906-1.906372 4.181874 32 6 0 0.519449-2.867947 3.164088 33 6 0 0.313288-2.459489 1.825222 34 1 0 0.102531 0.914694 2.335950 35 9 0 0.443137 0.370063 4.882258 36 6 0-0.010033 5.506971 0.130823 37 6 0 1.386238 6.165581 0.202615 38 1 0 1.955421 5.789718 1.079917 39 1 0 1.292762 7.268666 0.311297 40 1 0 1.966018 5.969229-0.724322 41 6 0-0.768504 5.872528 1.427617 42 1 0-0.250856 5.452788 2.316425 43 1 0-1.810002 5.488585 1.420112 44 1 0-0.830672 6.976358 1.549668 45 6 0-0.758286 6.113903-1.076530 46 1 0-0.231695 5.868655-2.023565 47 1 0-0.820129 7.220553-0.987422 48 1 0-1.798450 5.732901-1.149999 49 6 0-6.252341 0.841020-0.200815 50 6 0-6.935252 0.224872 1.036328 51 1 0-6.891540-0.883022 1.016949 52 1 0-8.007172 0.519059 1.079998 53 1 0-6.441223 0.581048 1.966381 54 6 0-6.450724 2.379598-0.118314 55 1 0-5.992010 2.795467 0.805243 56 1 0-7.531408 2.641270-0.093460 57 1 0-6.011451 2.889844-1.003436 58 6 0-6.961797 0.358830-1.482681 59 1 0-6.918191-0.744719-1.583176 60 1 0-6.486528 0.812248-2.379909 61 1 0-8.034116 0.654438-1.474144 62 6 0 6.081112 0.985085-0.588884 63 6 0 6.426993 1.687061 0.742794 64 1 0 5.779986 2.570367 0.922472 65 1 0 7.480831 2.043800 0.736017 66 1 0 6.305848 0.984725 1.595450 67 6 0 7.089484-0.172660-0.780869 68 1 0 7.019643-0.904920 0.052088 69 1 0 8.133196 0.212102-0.797761 70 1 0 6.914322-0.697497-1.744686 71 6 0 6.283160 1.975596-1.756859 72 1 0 5.634161 2.869804-1.654637 73 1 0 6.051158 1.484452-2.726339 74 1 0 7.335703 2.333482-1.792117 75 9 0 0.676882-4.167484 3.506964 76 1 0 2.164599 3.751272-0.069820 77 1 0 3.816341 2.438841-0.308255 78 6 0-0.467141-5.681488-2.922445 79 1 0 0.716637-2.218739 5.206997 80 1 0-0.373573-6.772591-2.728659 81 1 0 0.268821-5.403051-3.704772 82 1 0-1.493650-5.483729-3.295642 83 1 0-3.936740 2.412052-0.140333 84 1 0-2.204633 3.748310-0.029707 85 1 0-5.167074-1.728559-0.347043 86 1 0-2.784899-2.393519-0.442413 87 1 0 2.695445-2.382965-0.791673 88 1 0 5.010495-1.721922-0.830986 89 1 0 0.140932-6.596468-0.420851 90 1 0-0.501814-2.979244-2.645925 91 7 0-0.333099-0.318603-3.678652 S43

DFT Results for 3c SCF Energy: -2401.6547065 a.u. Frontier Orbitals HOMO -8.731 ev LUMO -5.210 ev S44

Singlet Optimized Coordinates for 3c --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0-1.199889 3.474527-0.234119 2 6 0-3.606062 1.690745-0.383041 3 6 0-2.349351 1.240019-0.404090 4 6 0-1.181483 2.136304-0.313773 5 6 0 0.109841 4.225491-0.171445 6 6 0 1.383070 3.411487-0.229747 7 7 0 0.041480 1.465689-0.324152 8 6 0 1.296839 2.075995-0.310887 9 6 0-4.734695 0.720448-0.470977 10 6 0-4.361268-0.747181-0.546800 11 6 0-3.068614-1.137957-0.557889 12 7 0-2.040745-0.164966-0.512883 13 6 0 2.420759 1.124619-0.403804 14 6 0 3.699233 1.512680-0.382605 15 6 0 4.780855 0.492515-0.476484 16 7 0 2.044923-0.262948-0.518969 17 6 0 3.026137-1.283862-0.564767 18 6 0 4.337261-0.956892-0.554042 19 77 0-0.005589-0.510747-0.549946 20 6 0-0.006991-0.213819-2.704247 21 7 0-0.054559-2.589226-0.670477 22 6 0-0.066113-3.283751 0.591386 23 6 0-0.099844-4.644223 0.630835 24 6 0-0.120736-5.434793-0.627856 25 6 0-0.102906-4.654204-1.916409 26 6 0-0.072381-3.305758-1.894293 27 1 0-0.113992-5.230833 1.538380 28 6 0-0.009454-1.020160 1.548223 29 6 0 0.009771-0.127259 2.630008 30 6 0-0.004011-0.620843 3.950624 31 6 0-0.036456-1.995187 4.201345 32 6 0-0.055773-2.898273 3.145515 33 6 0-0.042707-2.417288 1.805983 34 9 0 0.036590 1.205936 2.423045 35 9 0 0.011659 0.239290 4.997513 36 6 0 0.098554 5.767127-0.107387 37 6 0 1.526244 6.352460-0.065081 38 1 0 2.083735 5.984011 0.824109 39 1 0 1.483665 7.458411-0.006283 40 1 0 2.098568 6.083498-0.980860 41 6 0-0.646405 6.191508 1.171991 42 1 0-0.140369 5.780474 2.073649 43 1 0-1.695430 5.826734 1.177346 44 1 0-0.671468 7.296372 1.253288 45 6 0-0.621612 6.321117-1.353899 46 1 0-0.097133 6.010938-2.284755 47 1 0-0.648812 7.429361-1.318950 48 1 0-1.670013 5.960939-1.420156 49 6 0-6.218881 1.179359-0.491274 50 6 0-6.953213 0.543795 0.704093 51 1 0-6.906475-0.564165 0.667249 52 1 0-8.023296 0.838197 0.701692 53 1 0-6.501211 0.874123 1.665476 54 6 0-6.369640 2.718635-0.391127 55 1 0-5.935557 3.107157 0.556933 56 1 0-7.441858 3.005697-0.409826 57 1 0-5.871892 3.230997-1.244329 58 6 0-6.856895 0.716935-1.814484 59 1 0-6.810102-0.386678-1.922766 60 1 0-6.330833 1.168872-2.684663 61 1 0-7.923979 1.018804-1.856450 62 6 0 6.260939 0.969323-0.496842 63 6 0 6.570388 1.753394 0.798292 64 1 0 5.922864 2.649357 0.906939 65 1 0 7.624033 2.105023 0.797194 66 1 0 6.417064 1.112530 1.693345 67 6 0 7.235270-0.220853-0.593460 68 1 0 7.121142-0.900659 0.278601 69 1 0 8.284797 0.139772-0.608391 70 1 0 7.062028-0.802154-1.524983 71 6 0 6.481971 1.885150-1.721425 72 1 0 5.835425 2.788158-1.685850 73 1 0 6.255281 1.342202-2.664703 74 1 0 7.536229 2.231732-1.763103 75 9 0-0.089931-4.218429 3.456458 76 1 0 2.336667 3.906477-0.217162 77 1 0 3.966386 2.557899-0.299957 78 1 0-5.148008-1.483378-0.593536 79 1 0-2.814103-2.183882-0.607780 80 8 0-0.116908-5.290429-3.114164 81 9 0-0.051506-2.459087 5.480474 82 1 0-0.147950-6.547325-0.589892 83 1 0-0.059239-2.759014-2.815407 84 1 0-3.807987 2.748076-0.302347 85 1 0-2.123142 4.028670-0.224841 86 1 0 2.722670-2.316575-0.614905 87 1 0 5.078953-1.735751-0.601979 88 6 0-0.145993-6.661567-3.270367 89 1 0-0.149253-6.885324-4.353723 90 1 0-1.064317-7.093354-2.815073 91 1 0 0.752188-7.131772-2.812991 92 7 0-0.007604-0.048645-3.862210 S45