Supporting Information

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1 Supporting Information Dithieno-Fused Polycyclic Aromatic Hydrocarbon with a Pyracylene Moiety: Strong Antiaromatic Contribution to the Electronic Structure Chaolumen, Michihisa Murata,*,, Atsushi Wakamiya, and Yasujiro Murata*, Institute for Chemical Research, Kyoto University, Uji, Kyoto , Japan PRESTO, Japan Science and Technology Agency (JST), Honcho, Kawaguchi, Saitama , Japan mmurata@scl.kyoto-u.ac.jp; yasujiro@scl.kyoto-u.ac.jp Contents 1. General S1 2. Computational Methods S2 3. Synthesis S3 4. NMR Spectra S6 5. X-ray Crystallographic Analysis S9 6. Photophysical Properties S11 7. Cyclic Voltammograms S13 8. DFT Calculations S15 9. Optimized Geometries S References S26

2 1. General Melting points (mp) were measured on a Yanaco MP-S3 instrument. The 1 H and 13 C NMR measurements were carried out with a JEOL ECA 500 instrument or a Bruker Avance III 600US instrument. The NMR chemical shifts are reported in ppm with reference to residual protons and carbons of CDCl 3 (δ 7.26 ppm in 1 H NMR, δ ppm in 13 C NMR) and CD 2 Cl 2 (δ 5.32 ppm in 1 H NMR, δ 53.5 ppm in 13 C NMR). UV-vis absorption spectra were measured with a Shimadzu UV-3150 spectrometer. APCI mass spectra were measured on a Bruker microtof-q II spectrometer. Cyclic voltammetry (CV) was performed on a BAS ALS620A electrochemical analyzer. The CV cell consisted of a glassy carbon electrode, a Pt wire counter electrode, and an Ag/AgNO 3 reference electrode. The measurements were carried out under an argon atmosphere using a CH 2 Cl 2 solution of a sample with a concentration of 1 mm and 0.1 M tetrabutylammonium hexafluorophosphate ((n- Bu) 4 N + PF 6 ) as a supporting electrolyte. The redox potentials were calibrated with ferrocene as an internal standard. Tetracene, and bis(pinacolato)diboron were purchased from Tokyo Chemical Industry Co., Ltd. N-Bromosuccinimide (NBS), palladium(ii) acetate, potassium acetate, potassium phosphate tribasic, dimethylformamide (DMF), 2-bromo-5- methylthiophene, p-chloranil, and trifluoromethanesulfonic acid (TfOH) were purchased from Wako Pure Chemical Industries, Ltd. NBS was recrystallized from water before use. 2- Dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) and iron (III) chloride were purchased from Sigma-Aldrich Co. LLC. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was purchased from Nacalai Tesque, Inc. 5,11-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2yl)tetracene was prepared according to the literature. [1] Thin layer chromatography (TLC) was performed on glass plates coated with 0.25 mm thick silica gel 60F-254 (Merck). Column chromatography was performed using PSQ 60B (Fuji Silysia Chemical). All reactions were carried out under an argon atmosphere. S1

3 2. Computational Methods All calculations were conducted using the Gaussian 09 program. [2] The geometries were optimized with the B3LYP functional and 6-31G* basis sets without any symmetry assumptions. NMR chemical shifts were calculated at the B3LYP/6-311G** level using the optimized structures at the B3LYP/6-31G* level. NICS(0) [3] values were calculated at the HF/6-311+G** level using the optimized structures at the B3LYP/6-31G* level. The anisotropy of current-induced density (ACID) [4] was calculated at the HF/6-311+G** level using the optimized structures at the B3LYP/6-31G* level with the ACID program implemented in the Gaussian 09 program (NMR = CSGT IOp(10/93=1)). Optical transitions with oscillator strength were calculated at the TD-CAM-B3LYP/6-31G* using the optimized structures at the B3LYP/6-31G* level. Frequency calculations were conducted at the same level of theory as the geometry optimizations. S2

4 3. Synthesis Synthesis of 5,11-dithienyltetracene 3 3: To a mixture of 5,11-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)tetracene (47 mg, 0.10 mmol), 2-bromo-5-methylthiophene (53 mg, 0.29 mmol), Pd 2 (dba) 3 CHCl 3 (4 mg, 4 µmol), Sphos (5 mg, 12 µmol) and K 3 PO 4 (152 mg, 0.59 mmol) were added degassed toluene (1.0 ml) and distilled water (0.10 ml) in a Schlenk tube and the solution was stirred at 110 C for 5 h. After cooling to room temperature, to the resulting mixture was added distilled water. The aqueous layer was extracted with CH 2 Cl 2 and the combined organic layer was washed with brine. After drying with Na 2 SO 4, the solvent was evaporated. Then, the crude product was purified by silica gel column chromatography using n-hexane/ch 2 Cl 2 (5:1) as an eluent. The solvent was evaporated to give 3 (20 mg, mmol) in 48% yield as a yellow solid. 3: mp > 300 C; 1 H NMR (500 MHz, CDCl 3 ): δ 8.67 (s, 2H), (m, 4H), (m, 4H), 7.05 (d, J = 3.5 Hz, 2H), (m, 2H); 13 C NMR (126 MHz, CDCl 3 ): δ , , , , , , , , , , , , , 15.70; HRMS (+APCI): [M+H] + calcd. for C 28 H 21 S , found S3

5 Synthesis of compound 4 S S p-chloranil (1.0 equiv) S TfOH / CH 2 Cl 2 (1 / 100) 0 C, 10 min S 3 4, 53% 4: A mixture of 5,11-dithienyltetracene derivative 3 ( 42 mg, 0.10 mmol) and p-chloranil (25 mg, 0.10 mmol) was dissolved in dry dichloromethane (10 ml) in a 50 ml 2-necked flask. TfOH (0.10 ml) was injected through a syringe. The solution was stirred at 0 C for 10 min under argon and quenched by excessive hydrazine. The resulting mixture was extracted with CH 2 Cl 2 and the combined organic layer was washed with brine. After drying with Na 2 SO 4, the solvent was evaporated. Then, the crude product was purified by silica gel column chromatography using n-hexane/ch 2 Cl 2 (5:1) as an eluent. The solvent was evaporated to give 4 (22 mg, mmol) in 53% yield as a deep purple solid. 4: mp C; 1 H NMR (500 MHz, CD 2 Cl 2 ): δ 8.49 (s, 1H), 8.46 (d, J = 8.5 Hz, 1H), (m, 2H), 7.99 (d, J = 8.5 Hz, 1H), (m, 2H), 7.56 (s, 1H), (m, 2H), 7.14 (d, J = 3.5 Hz, 1H), (m, 1H), 2.75 (s, 3H), 2.69 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , , , , , 16.63, (one sp 2 signal was overlapped with other signal); HRMS (+APCI): [M+H] + calcd. for C 28 H 19 S , found S4

6 Synthesis of compound 5 Synthesis of 5: A mixture of 5,11-dithienyltetracene derivative 3 (42 mg, 0.10 mmol) and p- chloranil (49 mg, 0.20 mmol) was dissolved in dry dichloromethane (10 ml) in a 50 ml 2- necked flask. TfOH (0.10 ml) was injected through a syringe. The solution was stirred at 0 C for 10 min under argon and quenched by excessive hydrazine. The solvent was evaporated and the product was further washed by water, methanol and acetone. Then the product was dried under vacuum to give 5 (24 mg, mmol) in 57% yield as a dark blue solid. 5: mp > 300 C; 1 H NMR (500 MHz, CS 2 -CD 2 Cl 2 (5:1)): δ (m, 2H), (m, 2H), (m, 4H), 6.50 (s, 2H), 2.40 (s, 6H); HRMS (+APCI): [M+H] + calcd. for C 28 H 17 S , found We could not observe 13 C NMR signals of 5 likely due to severe broadening caused by the aggregation. S5

7 4. NMR Spectra 1 H NMR spectrum of 3 (500 MHz, CDCl 3 ). abundance abundance X : parts per Million : Proton CHCl H 2 O X : parts per Million : Proton C NMR spectrum of 3 (126 MHz, CDCl 3 ). (thousandths) (thousandths) X : parts per Million : Carbon CDCl X : parts per Million : Carbon S6

8 1 H NMR spectrum of 4 (500 MHz, CD 2 Cl 2 ). abundance abundance X : parts per Million : Proton X : parts per Million : Proton CHDCl H 2 O 13 C NMR spectrum of 4 (126 MHz, CDCl 3 ). abundance (thousandths) X : parts per Million : Carbon CDCl X : parts per Million : Carbon S7

9 1 H NMR spectrum of 5 (500 MHz, CS 2 -CD 2 Cl 2 (5:1)) abundance abundance X : parts per Million : Proton CHDCl 2 H 2 O X : parts per Million : Proton S8

10 5. X-ray Crystallographic Analysis Crystallographic data have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC (3) and CCDC (5). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via Compound 3: Intensity data were collected at 100 K on a Bruker Single Crystal CCD X-ray Diffractometer (SMART APEX II) with Mo Kα radiation (λ = Å) and graphite monochromater. A total of 4977 reflections were measured at the maximum 2θ angle of 50.0, of which 1896 were independent reflections (R int = ). The structure was solved by direct methods (SHELXS-97 [5] ) and refined by the full-matrix least-squares on F 2 (SHELXL- 97 [5] ). 5-Methylthienyl group C10-C11-C12-C13-S1-C14 was disordered, which was solved using appropriate models. Thus, two sets of 5-Methylthienyl groups, i.e. (C10A-C11A- C12A-C13A-S1A-C14A) and (C10B-C11B-C12B-C13B-S1B-C14B) were placed and their occupancies were refined to be 0.61 and 0.39, respectively. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed using AFIX instructions. The crystal data are as follows: C 28 H 20 S 2 ; FW = , crystal size mm 3, Monoclinic, C2/c, a = (3) Å, b = (12) Å, c = (2) Å, β = (2), V = (6) Å 3, Z = 4, D c = g cm 3. The refinement converged to R 1 = , wr 2 = (I > 2σ(I)), GOF = Figure S1. The ORTEP drawing (50% probability for thermal ellipsoids) of 3. S9

11 Compound 5: Intensity data were collected at 100 K on a Bruker Single Crystal CCD X-ray Diffractometer (SMART APEX II) with Mo Kα radiation (λ = Å) and graphite monochromater. A total of 4121 reflections were measured at the maximum 2θ angle of 50.1, of which 1645 were independent reflections (R int = ). The structure was solved by direct methods (SHELXS-97 [5] ) and refined by the full-matrix least-squares on F 2 (SHELXL- 97 [5] ). The fused thiophene moiety C10-C11-C12-C13-S1-C14 was disordered, which was solved using appropriate models. Thus, two sets of the fused thiophene moieties, i.e. (C10- C11-C12A-C13-S1A-C14A) and (C10-C11-C12B-C13-S1B-C14B) were placed and their occupancies were refined to be 0.81 and 0.19, respectively. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed using AFIX instructions. The crystal data are as follows: C 28 H 16 S 2 ; FW = , crystal size mm 3, monoclinic, P2 1 /n, a = (15) Å, b = (9) Å, c = (3) Å, β = (19), V = 933.8(3) Å 3, Z = 2, D c = g cm 3. The refinement converged to R 1 = , wr 2 = (I > 2σ(I)), GOF = Figure S2. (a) The ORTEP drawing (50% probability for thermal ellipsoids) and (b) packing within the crystal of 5. S10

12 6. Photophysical Properties Figure S3. UV-vis absorption spectra of 3, 4, and 5 in toluene with their pictures. S11

13 S Me n-c 5 H 11 5 S Me n-c 5 H x 10 4 M 1c 2.18 x 10 4 M 3.0 max = 613 nm log = / 10 4 M 1 cm max = 608 nm log = Wavelength / nm Figure S4. UV-vis absorption spectra of 5 and 1c in toluene with their pictures. S12

14 7. Cyclic Voltammograms Figure S5. (a) Cyclic voltammograms of 3, 4, and 5 in CH 2 Cl 2 (1 mm), measured with (n- Bu) 4 N + PF 6 (0.1 M) as a supporting electrolyte at a scan rate of 100 mv s 1. (b) Cyclic voltammograms of 5 and 1c. Oxidation waves were irreversible likely due to the aggregation or adsorption on the surface of electrode. S13

15 Figure S6. Cyclic voltammograms of 5 in CH 2 Cl 2 (1 mm) from the 1st-5th cycles, in the range of +0.5 to 1.5 V, measured with (n-bu) 4 N + PF 6 (0.1 M) as a supporting electrolyte at a scan rate of 100 mv s 1. S14

16 8. DFT Calculations Figure S7. 1 H NMR spectra simulated for 3, 4, 5, and 1a. Red, blue, pink, purple, black and green dots indicate the assignment of the proton signals (GIAO-B3LYP/6-311G**//B3LYP/6-31G*). S15

17 Figure S8. Pictorial presentation of the frontier orbitals with the energy levels (B3LYP/6-31G*) for 3, 4 and 5. Model structures without methyl groups were used. S16

18 Figure S9. Pictorial presentation of the frontier orbitals with the energy levels (B3LYP/6-31G*) for 1c and 5. S17

19 Table S1. Selected Electronic Transitions of 1c (TD-CAM-B3LYP/6-31G*//B3LYP/6-31G*) excited state energy (ev) wavelength (nm) oscillator strength (f) contributed MOs HOMO-1 LUMO HOMO LUMO HOMO 2 LUMO HOMO 1 LUMO HOMO LUMO Table S2. Selected Electronic Transitions of 5 (TD-CAM-B3LYP/6-31G*//B3LYP/6-31G*) excited state energy (ev) wavelength (nm) oscillator strength (f) contributed MOs HOMO LUMO HOMO 1 LUMO HOMO 3 LUMO HOMO 2 LUMO S18

20 Figure S10. NICS (0) values and ACID plots for (a) model compounds 5 and (b) dibenzopyracylene (HF/6-311+G**//B3LYP/6-31G*). S19

21 9. Optimized Geometries Compound 1c (B3LYP/6-31G*) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S20

22 S21

23 Compound 3 (B3LYP/6-31G*) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S22

24 Compound 4 (B3LYP/6-31G*) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S23

25 Compound 5 (B3LYP/6-31G*) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S24

26 Compound 5 (B3LYP/6-31G*) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S25

27 8. References [1] (a) Avlasevich, Y.; Müllen, K. Chem. Commun. 2006, (b) Papagni, A.; Trombini, C.; Lombardo, M.; Bergantin, S.; Chams, A.; Chiarucci, M.; Miozzo, L.; Parravicini, M. Organometallics 2011, 30, [2] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Mont-gomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Koba-yashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision E.01, Gaussian, Inc.; Wallingford, CT, [3] Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. J. R. v. E. J. Am. Chem. Soc. 1996, 118, [4] (a) Herges, R.; Geuenich, D. J. Phys. Chem. A 2001, 105, (b) Geuenich, D.; Hess, K.; Köhler, F.; Herges, R. Chem. Rev. 2005, 105, [5] Sheldrick, G. M. SHELX-97, Program for the Refinement of Crystal Structures; University of Gottingen: Gottingen, Germany, S26