From Arm-Chair to Zig-Zag Peripheries in. Nanographenes

Transcription

1 Supporting information for: From Arm-Chair to Zig-Zag Peripheries in Nanographenes Marcel Kastler, Jochen Schmidt, Wojciech Pisula, Daniel Sebastiani, Klaus Müllen* Max-Planck-Institute for Polymer esearch, Postfach 3148, D Mainz, Germany Experimental Details General Methods: Chemicals were obtained from Fluka, Aldrich, and ABC and used as received, unless otherwise specified. Column chromatography and TLC was performed with Merck silica gel 60 ( mesh) and Merck silica gel 60 F 254, respectively. 1 NM and 13 C NM spectra were recorded on a Bruker DPX 250, Bruker 300 AMX, Bruker DX 500 or Bruker DX 700 spectrometer with use of the solvent proton or carbon signal as an internal standard. Field Desorption (FD) mass spectra were obtained on a VG Instruments ZAB 2-SEFPD. MALDI-TOF mass spectra were measured using a Bruker eflex II-TOF spectrometer using a 337 nm nitrogen laser and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as matrix. Elemental analysis was carried out on a Foss eraeus Vario EL in the Institute for Organic Chemistry at the Johannes Gutenberg University, Mainz. The optical absorption measurements were performed at ambient temperature using a UV/vis/NI Perkin-Elmer Lambda 900 spectrometer. The photoluminescence in solution was recorded on a SPEX Fluorolog 2 type 212 steady-state fluorometer. The 2D-WAXS experiments were performed by means of a rotating anode (igaku 18 kw) X-ray beam with a pinhole collimation and a 2D Siemens detector. A double graphite monochromator for the Cu-K α radiation

2 (λ=0.154 nm) was used. All quantum chemical calculations have been performed with the program package GAUSSIAN. (Achtung, vollkommen gestört: Gaussian 98, evision A.7, M. J. Frisch, G. W. Trucks,. B. Schlegel, G. E. Scuseria, M. A. obb, J.. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr.,. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi,. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. abuck, K. aghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi,. Gomperts,. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. ead-gordon, E. S. eplogle, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1998.)) Synthesis: Tetra-(4,4,4,4 -dodecyl-)phenylbenzene 7 c g d f e j h k i = n o b a m l 200 mg 2,3,4,5-Tetrakis(4-dodecyl-phenyl)-cyclopentadienone (189 µmol) and 37 mg diphenyl acetylene 6 (208 µmol) were heated over night in 1 ml diphenylether to 280 C. The solvent was removed using high vacuum and the residue was purified utilizing preparative column chromatography (silica gel, eluent: low boiling

3 petroleum ether, dichloromethane = 9:1, f = 0.63) to afford 212 mg of the desired product as a colorless oil (93%, 175 µmol). MS (FD, 8kV): m/z (%) = (100%, M + ) (calc. for C = g mol -1 ) 1 NM (300 Mz, CD 2 Cl 2, 303K): δ = 6.75 (m, 10, a, b, c, d, e ), 6.61 (m, 8, f, g, h, i ), 6.55 (m, 8, j, k, l, m ), 2.26 (t, 8, 3 J(,) = 7.53 z, n ), (m, 40, -C 2 ), 0.80 (t, 12, 3 J(,) = 6.90 z, o ) 13 C NM (75 Mz, CD 2 Cl 2, 383K): δ = , , , , , , , , , , , , , , , , , , , 35.68, 35.61, 32.34, 31.70, 31.59, 30.12, 30.09, 29.92, 29.89, 29.78, 29.31, 29.20, 23.09, 14.27, 30.13, ,5,8,11-Tetradodecyl-hexa-peri-hexabenzocoronene 1b b d c e f a g = h i j k l 50 mg Tetra-(4,4,4,4 -dodecyl-)phenylbenzene 7 (41.4 µmol) were dissolved in 25 ml dichloromethane. A with dichloromethane saturated stream of argon was bubbled into the solution through a Teflon tube. A solution of 113 mg iron(iii) chloride (695 µmol) in 0.5 ml nitromethane was quickly added. After a reaction time of 45 minutes, the reaction was stopped with methanol. The precipitate was collected and washed extensively with aqueous hydrochloride acid and methanol. The crude product was recrystallized from toluene to afford 46 mg of the product as a yellow, waxy solid (93%, 38.5 µmol). MS (MALDI-TOF): m/z (%) = 1195 (33%), 1196 (33%), 1197 (21%), 1198 (8%), 1199 (4%) (calc. for C = g mol -1, isotope pattern: 1195 (36%), 1196 (37%), 1197 (19%), 1198 (6%), 1199 (2%)) 1 NM (500 Mz, C 2 D 2 Cl 4, 383K): δ = 8.77 (d, 2, 3 J(,) = 8.39 z, a ), 8.75 (d, 2, 3 J(,) = 8.34 z, c ), (m, 8, d, e, f, g ), 7.87 (t, 2, 3 J(,) =

4 7.56 z, b ), 3.15 (m, 8, h ), 2.05 (tt, 8, 3 J(,) = 6.95 z, i ), 1.66 (m, 8, j ), 1.55 (m, 8, k ), (m, 56, -C 2 -), 0.87 (t, 12, 3 J(,) = 6.56z, l ) 13 C NM (125 Mz, C 2 D 2 Cl 4, 383K): δ = , , , , , , , , , , , , , , , , , , 37.35, 37.32, 32.08, 30.06, 30.02, 29.97, 29.93, 29.84, 29.47, 22.77, UV/vis: λ / nm (ε / m 2 mol -1 ) = 342 (856), 361 (2043), 392 (663), 441 (27), 448 (25), 466 (9) DSC ( C): 147 (123) Elemental Analysis: 90.21% C, 9.49% (calc.: 90.39% C, 9.61% ) 4-ydroxy-phenanthrene f g e h d c i O j a b 500 mg 4-Methoxy-phenathrene 8 (2.40 mmol) were dissolved in 15 ml dichloromethane and cooled to -78 C ml Boron tribromide (1.20 g, 4.79 mmol) were added and the mixture was stirred over night at room temperature. The reaction was terminated by adding water. The organic phase was separated off and dried with magnesium sulfate. After having evaporated the solvent, the residue was purified using column chromatography (silica gel, eluent: hexane, ethyl acetate = 8:2, f = 0.2) to afford 403 mg of the desired compound as a colorless, crystalline solid (86%, 2.07 mmol). MS (FD, 8kV): m/z (%) = (M +, 100%) (calc. for C O= g mol -1 ) 1 NM (300 Mz, CD 2 Cl 2 ): δ = 9.64 (dd, 1, 3 J(,) = 8.26 z, 4 J(,) = 0.81 z, a ), 7.90 (dd, 1, 3 J(,) = 7.62 z, 4 J(,) = 1.51 z, d ), (m, 6, b, c, e, f, g, h ), 7.03 (dd, 1, 3 J(,) = 7.52 z, 4 J(,) = 1.29 z, i ), 5.89 (s, 1, j ) 13 C NM (75 Mz, CD 2 Cl 2 ): δ = (C-O)), , , , , , , , , , , , , Elemental Analysis: 86.43% C, 5.23% (calc.: 86.57% C, 5.19%, 8.24% O)

5 1,1,2,2,3,3,4,4,4-Nonafluoro-butane-1-sulfonic acid phenanthren-4- yl ester 9 d c e b f g h i O a S O O F F F F F F F F F 200 mg 4-ydroxy-phenanthrene (1.03 mmol) were dissolved in a mixture of 172 µl 1,1,2,2,3,3,4,4,4-Nonafluoro-butane-1-sulfonyl fluoride (1.24 mmol) and 6 ml dichloromethane and stirred over night. The reaction was stopped by adding water. The organic phase was separated, dried with magnesium sulfate and the solvent was evaporated in vacuo. The residue was purified using preparative column chromatography (silica gel, eluent: hexane, ethyl acetate = 8:2, f = 0.62) to obtain 457 mg of the desired material as a colorless oil (93%, 0.96 mmol). MS (FD, 8kV): m/z (%) = (M +, 100%) (calc. for C 18 9 F 9 O 3 S= g mol -1 ) 1 NM (300 Mz, CD 2 Cl 2 ): δ = 9.21 (dd, 1, 3 J(,) = 8.21 z, 4 J(,) = 1.00 z, a ), 7.95 (dd, 1, 3 J(,) = 7.41 z, 4 J(,) = 1.56 z, d ), 7.90 (dd, 1, 3 J(,) = 7.71 z, 4 J(,) = 1.52 z, g ), (m, 6, b, c, e, f, h, i ) 13 C NM (75 Mz, CD 2 Cl 2 ): δ = , , , , , , , , , , , (all Ar-C), , , , (nonaflat-c, coupling due to fluorine nuclei) 4-Ethynyltrimethylsilyl-phenanthrene f g e d c b a Si j h i 170 mg 1,1,2,2,3,3,4,4,4-Nonafluoro-butane-1-sulfonic acid phenanthren-4-yl ester 9 (0.36 mmol), 62 mg trimethylsilyl acetylene (0.18 ml, 0.63 mmol), 1.1 mg triphenylphosphine (4.2 µmol), and 0.8 mg copper(i) iodide (4.2 µmol) were dissolved in 5 ml triethyl-amine and degassed with three freeze-vacuum-thaw cycles.

6 Afterwards, 2.9 mg bis(triphenylphosphine)palladium(ii) chloride (4.2 µmol) were added and the mixture was stirred under argon at 80 C for 20 hours. The solvent was removed in vacuo and the residue was purified using preparative column chromatography (silica gel, eluent: hexane, ethyl acetate = 8:2, f = 0.74). After a recrystallization with ethanol as solvent, 86 mg of the analytically clean product were obtained as a colorless solid (87%, 0.31 mmol). MS (FS, 8kV): m/z (%) = (100%, M + ) (calc. for C Si = g mol -1 ) 1 NM (300 Mz, CD 2 Cl 2 ): δ = (m, 1, a ), (m, 3, b, d, e ), (m, 4, c, f, g, i ), 7.55 (t, 1, 3 J(,) = 7.84 z, h ), 0.44 (s, 9, j ) 13 C NM (75 Mz, CD 2 Cl 2 ): δ = , , , , , , , , , , , , , , (C CSi), (C CSi), (-Si(C 3 ) 3 ) Elemental Analysis: 83.08% C, 6.57% (calc.: 83.16% C, 6.61%, 10.23% Si) 4-Ethynyl-phenanthrene 10 f g e d c b a j h i 600 mg 4-Ethynyltrimethylsilyl-phenanthrene (2.19 mmol) were dissolved under gentle heating in 60 ml methanol and degassed. Afterwards, 1.2 g potassium carbonate (8.70 mmol) was added and the mixture was stirred at room temperature over night. The reaction was quenched by adding water. The product was extracted using dichloromethane. After removing the solvent from the organic phase in vacuo, the residue was recrystallized with ethanol to afford 420 mg of the desired product as yellowish needles (95%, 2.1 mmol) ( f = 0.67, hexane, ethyl acetate = 8:2). MS (EI): m/z (%) = 51.0 (1.21), 61.8 (2.37), 63.0 (1.96), 73.7 (4.57), 75.1 (3.37), 86.6 (8.42), 87.8 (3.90), 88.3 (3.86), 95.9 (1.07), 97.8 (3.24), 99.4 (18.44), (20.57), (8.33), (1.33), (2.74), (3. 19), (1.40), (4.92), (2.21), (1.37), (4.30), (38.48), (3.50), (100%), (13.65, M + ) (calc. for C = g mol -1 ) 1 NM (300 Mz, CD 2 Cl 2 ): δ = (m, 1, a ), (m, 3, d, b, e ), (m, 4, c, f, g, i ), 7.56 (t, 1, 3 J(,) = 7.85 z, h ), 3.80 (s, 1, j )

7 13 C NM (75 Mz, CD 2 Cl 2 ): δ = , , , , , , , , , , , , , , 86.58(-C C), (-C C) Elemental Analysis: 95.30% C, 4.88% (calc.: 95.02% C, 4.98% ) 4-(4,4,5,6 -Tetradodecyl-phenyl)-[1,1 ;4,1 ]terphenyl-2 yl)- phenanthrene 11 d e f g c h l k b j a i s v m q r n o t p u w 575 mg 2,3,4,5-Tetrakis(4-dodecyl-phenyl)-cyclopentadienone (544 µmol) and 100 mg 4-ethynyl-phenanthren 10 (494 µmol) were dissolved in 2 ml o-xylene and stirred at 160 C for 3 hours. The solvent was removed in vacuo and the residue was purified with preparative column chromatography (silica gel, eluent: hexane, ethyl acetate = 40:1, f = ) to afford the title compound as a colorless oil (95%, 469 µmol). MS (FD, 8kV): m/z (%) = (100%, M + ) (calc. for C = g mol -1 ) 1 NM (700 Mz, C 2 D 2 Cl 4, 353 K): δ = 8.16 (d, 1, 3 J(,) = 8.58 z, a ), 7.72 (d, 1, 3 J(,) = 7.80 z, d ), 7.63 (d, 1, 3 J(,) = 7.65 z, g ), 7.53 (2 x s, 2, e, f ), 7.50 (s, 1, j ), 7.43 (m, 2, c, i ), 7.37 (t, 1, 3 J(,) = 7.46 z, h ), 7.31 (t, 1, 3 J(,) = 7.32 z, b ), 7.00 (d, 2, 3 J(,) = 7.81 z, l ), 6.86 (d, 2, 3 J(,) = 7.84 z, k ), 6.79 (d, 2, 3 J(,) = 7.58 z, n ), 6.71 (d, 2, 3 J(,) = 7.64 z, m ), 6.66 (d, 2, 3 J(,) = 7.79 z, p ), 6.58 (d, 2, 3 J(,) = 7.80 z, o ), 6.37 (bd, 2, 3 J(,) = 6.34 z, r ), 6.27 (bd, 2, 3 J(,) = 6.20 z, q ), 2.47 (t, 2, 3 J(,) = 7.52 z, s ), 2.41 (t, 2, 3 J(,) = 7.34 z, t ), 2.31 (t, 2, 3 J(,) = 7.38 z, u ), 2.14 (t, 2, 3 J(,) = 7.32 z, v ), (m, 80, -C 2 -), 0.87 (m, 12, w )

8 13 C NM (175 Mz, C 2 D 2 Cl 4, 353 K): δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 35.30, 35.24, 35.14, , 31.70, 30.98, 30.92, 30.88, 30.69, 29.44, 29.32, 29.26, 29.21, 29.11, 29.00, 28.66, 28.62, 28.52, 29.48, 29.39, 22.44, ,11,14,17-Tetra(dodecyl)tetrabenzo[bc,ef,hi,uv]ovalene 2 b c d e f a g = i j h 32 mg 4-(4,4,5,6 -Tetradodecyl-phenyl)-[1,1 ;4,1 ]terphenyl-2 yl)-phenanthrene 11 (26 µmol) were dissolved in 25 ml dichloromethane. A with dichloromethane saturated stream of argon was bubbled into the solution through a Teflon tube. A solution of 140 mg iron(iii) chloride (0.86 mmol) in 1 ml nitromethane was quickly added. After a reaction time of 25 minutes, the reaction was stopped with methanol. The precipitate was filtered off and washed extensively with aqueous hydrochloride acid and methanol. The crude material was reprecipitated from methanol and recrystallized from toluene to afford 25 mg of the product as an orange, microcrystalline material (79%, 20.5 µmol). MS (MALDI-TOF): m/z (%) = 1219 (31%), 1220 (32%), 1221 (20%), 1222 (9%), 1223 (5%) (calc. for C = g mol -1, isotope pattern: 1219 (36%), 1220 (37%), 1221 (19%), 1222 (6%), 1223 (2%)) UV/vis: λ / nm (ε / m 2 mol -1 ) = 330 (1358), 347 (1726), 363 (2146), 380 (2048), 414 (885), 438 (974), 484 (82) 1 NM (700 Mz, TF, 60 C): δ = 8.79 (s, 2, f ), 8.55 (d, 2, 3 J(,) = 8.19 z, c ), 8.43 (m, 6, d, e, g ), 8.09 (d, 2, 3 J(,) = 8.66 z, b ), 8.00 (s, 2, a ), 3.09 (m, 8, i ), 2.06 (m, 8, j ), (m, 36, -C 2 -), 0.89 (t, 12, 3 J(,) =6.72 z, h )

9 13 C NM: could not be obtained due to the vanishing solubility in organic solvents even at elevated temperatures DSC ( C): 148 (98) Elemental Analysis: 90.61% C, 9.08% (calc.: 90.58% C, 9.42% ) 9,11-Bis-(4-bromo-phenyl)-cyclopenta[e]pyren-10-one 13 Br O Br 1.51 g Pyren-4,5-dione 12 (6.52 mmol) and 2.40 g 1,3-bis-(4-bromo-phenyl)-propan- 2-one (6.52 mmol) were suspended in 90 ml ethanol and heated to 80 C. Afterwards, a solution of 186 mg potassium hydroxide (3.31 mmol) in 0.9 ml methanol was added and the resulting solution was stirred for 25 minutes. The reaction was terminated with water. The mostly precipitated product was extracted with dichloromethane, which was dried afterwards with magnesium sulfate. After having removed the solvent, the material was purified using preparative column chromatography (neutral aluminum oxide, low boiling petroleum ether, dichloromethane = 3:1, f = 0.6) to afford 1.77 g of the thermally unstable title compound as a violet solid (47%, 3.14 mmol). The compound has to be quickly converted, because it is hardly stable in solution over longer periods of time. MS (FD, 8kV): m/z (%) = (100%, M + )(calc. for C Br 2 O = g mol -1 ) 9,12-Bis-(4-bromo-phenyl)-10-phenanthren-4-yl-benzo[e]pyrene 14 g f e d h c v i u a j b k Br t m s n r q p o l Br

10 333 mg 9,11-Bis-(4-bromo-phenyl)-cyclopenta[e]pyren-10-one 13 (0.59 mmol) and 119 mg 4-Ethynyl-phenanthrene 10 (0.59 mmol) were dissolved in 2 ml o-xylene and heated to 160 C for 5 hours. After having removed the solvent in vacuo, the residue was purified using preparative column chromatography (silica gel, low boiling petroleum ether, dichloromethane = 8:2, f = 0.34) to receive 327 mg of the desired polycyclic hydrocarbon as a white powder (75%, 0.44 mmol). MS (FD, 8kV): m/z (%) = (100%, M + ) (calc. for C Br 2 = g mol -1 ) 1 NM (500 Mz, C 2 D 2 Cl 4, 373 K): δ = 8.09 (d, 1, 3 J(,) = 8.05 z, t ), 8.00 (d, 1, 3 J(,) = 7.65 z, r ), 7.96 (d, 1, 3 J(,) = 8.89 z, p ), 7.93 (d, 1, 3 J(,) = 8.92 z, q ), 7.91 (d, 1, 3 J(,) = 7.58 z, m ), 7.83 (d, 1, 3 J(,) = 8.63 z, a ), 7.82 (d, 1, 3 J(,) = 8.17 z, o ), 7.77 (d, 1, 3 J(,) = 7.71 z, 4 J(,) = 1.28 z, g ), 7.74 (s, 1, j ), 7.67 (d, 1, 3 J(,) = 7.85 z, d ), 7.61 (d, 1, 3 J(,) = 8.83 z, f ), 7.56 (t, 1, 3 J(,) = 7.78 z, s ), 7.57 (d, 1, 3 J(,) = 8.80 z, e ), 7.50 (d, 2, 3 J(,) = 8.27 z, l ), 7.49 (t, 1, 3 J(,) = 7.70 z, h ), 7.44 (d, 1, 3 J(,) = 7.18 z, 4 J(,) = 1.35 z, i ), 7.37 (d, 2, 3 J(,) = 8.04 z, k ), 7.37 (t, 1, 3 J(,) = 7.87 z, n ), 7.26 (t, 1, 3 J(,) = 7.79 z, b ), 6.97 (t, 1, 3 J(,) = 8.36 z, 4 J(,) = 1.12 z, c ), 6.81 (bd, 2, v ), 6.57 (bd, 2, u ). 13 C NM (125 Mz, C 2 D 2 Cl 4, 403 K): δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Elemental Analysis: 74.70% C, 3.93% (calc.: 74.81% C, 3.55% )

11 9,12-Bis-(4-dodecyl-phenyl)-10-phenanthren-4-yl-benzo[e]pyrene 15 x q r s t p u o v n i m a j b k h c g f e d w l y 0.4 ml Dodeca-1-ene (300 mg, 1.8 mmol) were added to 4 ml of a 0.5 M solution 9- bora-bicyclo[3.3.1]nonane in TF and stirred at room temperature for 12 hours. A solution of 110 mg sodium hydroxide in 0.9 ml water was syringed to the reaction and allowed to react for an 20 minutes. Finally, 166 mg 9,12-Bis-(4-bromo-phenyl)- 10-phenanthren-4-yl-benzo[e]pyrene 14 (0.22 mmol) and 8 mg Dichloro[1,1 - bis(diphenyl-phosphino)ferrocene]palladium(ii) (11 µmol) were added to the reaction, which was stirred for additional five hours. After having removed the solvent in vacuo, the residue was purified using preparative column chromatography (silica gel, eluent: low boiling petroleum ether, dichloromethane = 9:1, f = 0.51) to obtain 184 mg of the desired product as a colorless oil (91%, 201 µmol). MS (FD, 8kV): m/z (%) = (100%, M + ) (calc. for C = g mol -1 ) 1 NM (500 Mz, C 2 D 2 Cl 4, 333 K): δ = 8.06 (d, 1, 3 J(,) = 8.03 z, o ), 7.96 (d, 1, 3 J(,) = 8.68 z, d ), 7.94 (d, 1, 3 J(,) = 7.67 z, q ), 7.92 (d, 1, 3 J(,) = 8.98 z, s ), 7.92 (d, 1, 3 J(,) = 8.97 z, r ), 7.86 (d, 1, 3 J(,) = 8.20 z, t ), 7.85 (d, 1, 3 J(,) = 7.60 z, v ), 7.72 (s, 1, j ), 7.70 (d, 1, 3 J(,) = 7.04 z, 4 J(,) = 2.33 z, g ), 7.63 (d, 1, 3 J(,) = 7.90 z, 4 J(,) = 1.11 z, a ), 7.56 (d, 1, 3 J(,) = 8.88 z, f ), 7.50 (d, 1, 3 J(, ) = 8.80 z, e ), 7.45 (t, 1, 3 J(,) = 7.84 z, p ), 7.44 (t, 1, 3 J(,) = 7.22 z, h ), 7.41 (d, 1, 3 J(,) = 7.17 z, i ), 7.34 (bd, 2, 3 J(,) = 6.44 z, k ), 7.28 (t, 1, 3 J(,) = 8.00 z, u ), 7.25 (t, 1, 3 J(,) = 6.91 z, b ), 7.14 (d, 2, 3 J(,) = 7.99 z, l ), 6.97 (t, 1, 3 J(,) = 8.55, 4 J(,) = 1.37 z, c ), 6.73 (bd, 1, n ), 6.63 (bd, 1 m ), 6.39 (bd, 1 n ), 6.29 (bd, 1, m ), 2.59 (t, 2, 3 J(,) = 7.63

12 z, x ), 2.25 (t, 1, 3 J(,) = 7.31 z, w ), (m, 40, -C 2 -), 0.81 (2xt, 6, 3 J(,) = 7.13 z, y ) 13 C NM (125 Mz, C 2 D 2 Cl 4, 373 K): δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 35.88, 35.49, 32.09, 32.07, 31.39, 31.20, 29.88, 29.84, 29.81, 29.69, 29.64, 29.47, 29.01, 22.80, ,17-Di(dodecyl)-dibenzo[hi,uv]phenanthro-(3,4,5,6-bcdef)-ovalene 3 b c d a = e f g h i 58.5 mg 9,12-Bis-(4-dodecyl-phenyl)-10-phenanthren-4-yl-benzo[e]pyrene 15 (63.7 µmol) were dissolved in 25 ml dichloromethane. A with dichloromethane saturated stream of argon was bubbled into the solution through a Teflon tube. A solution of 310 mg iron(iii) chloride (1.91 mmol) in 0.5 ml nitromethane was quickly added. After a reaction time of 60 minutes, the reaction was stopped with methanol. The precipitate was filtered off and washed extensively with aqueous hydrochloride acid and methanol to afford 52 mg of the product as an orange-red solid (90%, 57.3 µmol). MS (MALDI-TOF): m/z (%) = 906 (34%), 907 (33%), 908 (24%), 909 (9%) (calc. for C = g mol -1, isotope pattern: 906 (46%), 907 (36%), 908 (14%), 909 (4%)) 1 NM (500 Mz, C 2 D 2 Cl 4, 410 K): δ = 9.11 (bd, 4, 3 J(,)= 7.94 z, b ), 8.89 (bs, 4, a ), 8.40 (bd, 4, 3 J(,) = 8.91 z, c ), 8.32 (bs, 4, d ), 3.32 (t, 4, e ), 2.17 (m, 4, f ), 1.76 (m, 4, g ), 1.66 (m, 4, h ), (m, 32, -C 2 -), 0.89 (t, 6, 3 J(,) = 7.66 z, i ). 13 C NM: solubility too low to record spectrum with appropriate signal to noise ratio

13 DSC ( C): 226 (216) Elemental Analysis: 92.58% C, 7.16% (calc.: 92.67% C, 7.33% ) 1,1,2,2,3,3,4,4,4-Nonafluoro-butane-1-sulfonic acid 9,10-didodecylphenanthren-4-yl ester 17 e f g O F F F F O S O F F F F a F i = k h j d c b 100 mg 4-Methoxy-phenanthrene-9,10-dione 16 (420 µmol) were dissolved in 20 ml anhydrous TF. 1 ml of a 1M solution of dodecylmagnesium bromide in diethyl ether (1 mmol) was slowly added and the resulting mixture was stirred for 1 hour. The solvent was evaporated and the oily residue dissolved in 5 ml acetic acid. 1 ml of an aqueous iodic acid solution (58%) was added and the reaction was heated to reflux for 24 hours. The product was extracted with dichloromethane, carefully neutralized with aqueous sodium carbonate, dried with magnesium sulfate and evaporated in vacuo. The residue was dissolved in triethyl amine and 300 mg 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (1 mmol) were added to the solution, which was stirred at 50 C over night. The solvent was again removed in vacuo and the residue was purified using preparative column chromatography (flash silica gel, eluent: low boiling petroleum ether, dichloromethane = 9:1, f = 0.81) to yield 306 mg of the desired product as a colorless oil (90%, 377 µmol). MS (FD, 8kV): m/z (%) = (100%, M + ) (calc. for C F 9 O 3 S = g mol -1 ) 1 NM (250 Mz, CD 2 Cl 2 ): δ = 9.16 (d, 1, 3 J(,) = 8.38 z, 4 J(,) = 1.09 z, a ), 8.21 (d, 1, 3 J(,) = 8.18 z, 4 J(,) = 1.09 z, d ), 8.19 (d, 1, 3 J(,) = 7.82 z, 4 J(,) = 1.73 z, e ), (m, 4, b, c, f, g ), (m, 4, h ), (m, 4, i ), (m, 4, j ), (m, 32, -C 2 -), 0.95 (t, 6, 3 J(,) = 6.88 z, k ) 13 C NM (63 Mz, CD 2 Cl 2 ): δ = , , , , , , , , , , , , , (C,F coupling), (C,F coupling), (C,F coupling), (C,F coupling), 32.51, 31.10, 31.01, 30.90, 30.85, 30.38, 30.26, 30.12, 30.02, 29.95, 23.25,

14 18 F NM (471 Mz, CD 2 Cl 2 ): δ = , , , (fluorobenzene as standard) 2-(9,10-Didodecyl-phenanthren-4-yl)-4,4,5,5-tetramethyl- [1,3,2]dioxaborolane 18 e f g a O B O h = i j k l d c b 90 mg 1,1,2,2,3,3,4,4,4-Nonafluoro-butane-1-sulfonic acid 9,10-didodecylphenanthren-4-yl ester 17 (123 µmol), 47 mg bispinacolatodiborane (184 µmol), and 72.4 mg potassium acetate (738 µmol) were dissolved in 3 ml anhydrous DMF and degassed mg Tetrakis-(triphenylphosphino)-palladium(0) (12.3 µmol) were added and the resulting mixture was stirred over night at 90 C. The product was extracted with ethyl acetate. The organic phase was extensively washed with water, dried over magnesium sulfate and evaporated. The residue was purified using preparative column chromatography (flash silica gel, eluent: hexane, ethyl acetate = 20:1, f = 0.33) to afford 57 mg of the title compound as a colorless oil (72%, 88.9 µmol). MS (FD, 8kV): m/z (%) = (100%, M + ) (calc. for C BO 2 = g mol -1 ) 1 NM (250 Mz, CD 2 Cl 2 ): δ = 8.44 (d, 1, 3 J(,) = 8.19 z, a ), 8.23 (d, 1, 3 J(,) = 8.36 z, d ), 8.18 (d, 1, 3 J(,) = 8.39 z, e ), 7.84 (d, 1, 3 J(,) = 6.81 z, g ), (m, 2, b, c ), 7.55 (t, 1, 3 J(,) = 7.62 z, f ), (m, 4, i ), (m, 4, j ), (m, 4, k ), 1.49 (s, 12, h ), (m, 32, -C 2 -), 0.97 (t, 6, 3 J(,) = 6.87 z, l ) 13 C NM (63 Mz, CD 2 Cl 2 ): δ = , , , , , , , , , , , , , 84.71, 32.67, 31.53, 31.38, 31.07, 30.45, 30.24, 30.11, 30.01, 29.95, 25.17, 23.42,

15 1,3,5-Tris-(9,10-bisdodecyl-phenanthren-4-yl)-benzene and 1- Bromo-3,5-Bis-(9,10-bisdodecyl-phenanthren-4-yl)-benzene 21 = a b 1.40 g 2-(9,10-Didodecyl-phenanthren-4-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane 18 (2.18 mmol), 114 mg 1,3,5-tribromobenzene (0.34 mmol), and 688 mg barium hydroxide octahydrate (2.18 mmol) were dissolved in a mixture of 6 ml dimethoxyethane and 1 ml water and degassed mg tetrakis- (triphenylphosphine)-palladium(0) (17.0 µmol) were added and the mixture was refluxed for 27 hours. The solvent was evaporated and the residue was purified using preparative column chromatography (flash silica gel, eluent: low boiling petroleum ether, dichloromethane (20:1), f = 0.48) to afford 44.0 mg of the title compound (8%, 27.2 µmol) and 217 mg of the double reacted compound 1-bromo-3,5-Bis-(9,10- bisdodecyl-phenanthren-4-yl)-benzene 19 as side product, both as colorless oils. MS (MALDI-TOF, dithranol): m/z (%) = (M + ), (M + + Na + ) (calc. for C = g mol -1 ) 1 NM (250 Mz, CD 2 Cl 2 ): substance formed stable atropisomers, which isomerize around 180 C in odcb. owever, odcb covers most of the aromatic resonance, therefore, the resonances are given for the room temperature spectrum of the two atropisomers (ratio: 1:2) in CD 2 Cl (d, 0.6, 3 J(,) = 8.71 z), 8.39 (d, 0.82, 3 J(,) = 8.48 z), 8.21 (d, 0.41, 3 J(,) = 8.17 z), (m), 7.76 (d, 0.41, 3 J(,) = 8.49 z), (m), (t, 0.83, 3 J(,) = 7.55 z) (integration aromatic region = 24 ), (m, 12, a ), (m, 120, -C 2 -), 0.79 (t, 18, 3 J(,) = 6.72 z, b ) 13 C NM: could not be obtained resolved, see main text

16 5,6,11,12,17,18-exa-dodecyl-diphenanthro[3,4,5,6-uvabc;3',4',5',6'- efghi]ovalene 5 = c d e a b 10.5 mg 1,3,5-Tris-(9,10-bisdodecyl-phenanthren-4-yl)-benzene 21 (6.52 µmol) were dissolved in 25 ml dichloromethane. A with dichloromethane saturated stream of argon was bubbled into the solution through a Teflon tube. A solution of 38.0 mg iron(iii) chloride (235 µmol) in 0.1 ml nitromethane was quickly added. After a reaction time of 60 minutes, the reaction was stopped with methanol. The precipitate was filtered off and washed extensively with aqueous hydrochloride acid and methanol. epetitive reprecipitation gave 8.72 mg of the desired product as an orange material (83%, 5.43 µmol). MS (MALDI-TOF): m/z (%) = 1603 (30%), 1604 (34%), 1605 (22%), 1606 (10%), 1607 (4%) (calc. for C = g mol -1, Isotope pattern: 1603 (26%), 1604 (35%), 1605 (24%), 1606 (11%), 1607 (3%)) UV/vis: λ / nm (ε / m 2 mol -1 ) = 379 (1108), 397 (2509), 436 (903) 1 NM (500 Mz, TF, CS 2 ): 8.50 (bd, 6, a ), 8.20 (bd, 6, b ), 3.33 (bt, 12, c ), 2.09 (m, 12, d ), (m, 108, -C 2 -), 0.98 (bt, 18, 3 J(,) = 6.71 z, e ) (solubility of the compound is very low, NM resonances are broad because of self-association phenomena) 13 C NM: could not be obtained, because substance is hardly soluble DSC ( C): 48 (22) Elemental Analysis: 89.76% C, 10.04% (calc % C, 10.18% )

17 1,3-Bis-(9,10-bisdodecyl-phenanthren-4-yl)-5-(biphenyl-2-yl)- benzene 20 b a = c d e f 335 mg 2-biphenylboronic acid (1.69 mmol), 200 mg 1-bromo-3,5-Bis-(9,10- bisdodecyl-phenanthren-4-yl)-benzene 19 (169 µmol), and 688 mg barium hydroxide octahydrate (2.18 mmol) were dissolved in a mixture of 6 ml dimethoxyethane and 1 ml water and degassed mg tetrakis-(triphenylphosphine)-palladium(0) (17.0 µmol) were added and the mixture was refluxed for 6 hours. The solvent was evaporated and the residue was purified using preparative column chromatography (silica gel, eluent: low boiling petroleum ether, dichloromethane (20:1), f = 0.48) to afford 149 mg of the title compound as a colorless oil (71%, 120 µmol). MS (FS, 8kV): m/z (%) = (100%, M + ) (calc. for C = g mol -1 ) 1 NM (500 Mz, C 2 D 2 Cl 4 ): 8.31 (d, 1, 3 J(,) = 7.83 z, a ), (m, 4), 7.93 (d, 1, 3 J(,) = 8.12 z, b ), (m, 20), 3.07 (m, 8, c ), 1.68 (m, 8, d ), 1.54 (m, 8, e ), (m, 64, -C 2 -), 0.86 (t, 12, 3 J(,) = 6.89 z, f ) 13 C NM: carbon resonances are broad and not very well resolved, because rotation around the central phenyl ring is limited

18 5,6,17,18-Tetra-dodecyl-dibenzo[ef,hi]phenanthro[3,4,5,6- u,v,a,b,c]ovalene 4 f e d c b g a = i j h 50.2 mg 1,3-Bis-(9,10-bisdodecyl-phenanthren-4-yl)-5-(biphenyl-2-yl)-benzene 20 (39.9 µmol) were dissolved in 45 ml dichloromethane. A with dichloromethane saturated stream of argon was bubbled into the solution through a Teflon tube. A solution of 233 mg iron(iii) chloride (1.44 mmol) in 0.5 ml nitromethane was quickly added. After a reaction time of 60 minutes, the reaction was stopped with methanol. The precipitate was filtered off and washed extensively with aqueous hydrochloride acid and methanol. epetitive reprecipitation into methanol gave 45.2 mg of the desired product as an orange-yellow material (91%, 36.3 µmol). MS (MALDI-TOF): m/z (%) = 1243 (31%), 1244 (35%), 1245 (23%), 1246 (9%), 1247 (3%) (calc. for C = g mol -1, Isotope pattern: 1243 (35%), 1244 (36%), 1245 (19%), 1246 (7%), 1247 (2%)) UV/vis: λ / nm (ε / m 2 mol -1 ) = 332 (538), 353 (917), 372 (1329), 388 (2000), 422 (648), 448 (877), 469 (444), 490 (150) 1 NM (500 Mz, C 2 D 2 Cl 4, 413 K): 9.15 (db, 2, a ), 9.04 (tb, 2, b ), 8.93 (db, 2, c ), 8.47 (db, 2, d ), 8.15 (db, 2, e ), 8.09 (db, 2, f ), 7.87 (db, 2, g ), 3.69 (tb, 4, h ), 3.46 (tb, 4, h ), 2.15 (m, 4, i ), 2.03 (m, 4, i ), (m, 72, -C 2 -), 0.92 (tb, 12, j ) ( 3 J(,) couplings could not be resolved, resonances are broadened because of self-aggregation phenomena) 13 C NM: could not be obtained, because substance is hardly soluble DSC ( C): 173, 210 (144) Elemental Analysis: 89.43% C, 10.27% (calc % C, 9.24% )

19 Figure S1: 1 NM spectrum of 11, recorded in 1,1,2,2-tetrachloroethane-d 2 at 80 C. Figure S2: MALDI-TOF spectrum of 2, using solid state preparation with TCNQ as the matrix substance; inset: experimentally determined (black) and simulated (red bars) isotope pattern.

20 Figure S3: MALDI-TOF spectrum of 3, using solid state preparation with TCNQ as the matrix substance; inset: experimentally determined (black) and simulated (red bars) isotope pattern. Figure S4: 1 NM of 3, recorded in 1,1,2,2-tetrachloroethane-d 2 at 137 C (55000 scans)

21 Figure S5: MALDI-TOF spectrum of 4, using solid state preparation with TCNQ as the matrix substance; inset: experimentally determined (black) and simulated (red bars) isotope pattern; red arrow makes an impurity, which could not be assigned nor detected in the NM. Figure S6: Simulated atropisomers (molecular mechanics, MMFF), alkyl substituents are omitted for clarity.

22 Figure S7: Temperature dependent 1 NM spectra of 21, revealing isomerization of the atropisomers. Figure S8: MALDI-TOF spectrum of 5, using solid state preparation with TCNQ as the matrix substance; inset: experimentally determined (black) and simulated (red bars) isotope pattern.

23 Table S1: Summary of the unit cells and packing parameters for each derivative and phase. Derivative Phase 2D unit cell Packing parameters / nm 1a C r orthogonal a = 6.1 b = 2.38 Col ho hexagonal a = b C r pseudo-hexagonal a = 3.07 b = 1.76 Col ho hexagonal a = C r cubic a = 3.25 Col ho hexagonal a = C r cubic a = C r cubic a = 3.38 Col co cubic a = C r a = 2.56 Col ho hexagonal a = 2.91 Calculation Section:

24 Table S2: Comparison between the calculated excitation energies (E) and oscillator strengths (f) and the experimentally determined energies of the PAs 1-5. transition E(eV) exp. E(eV) calc. f (calc) 1 α p a 0.00 β α p b β α p c 0.26 β α p d 0.18 β α p e β a wavefunction composition: (-1 L+1), 0.49 ( L) b wavefunction composition: 0.27 (-1 L+1), 0.11 (-1 L+2), 0.62 ( L) c wavefunction composition: (-1 L+1), 0.63 ( L) d wavefunction composition: (-1 L+1), 0.64 ( L) e wavefunction composition: 0.50 (-1 L+1), 0.50 ( L)

25 exa-peri-hexabenzocoronene (1): OMO-1 OMO LUMO LUMO+1

26 Tetrabenzo[bc,ef,hi,uv]ovalene (2) OMO-1 OMO LUMO LUMO+1

27 Dibenzo[hi,uv]phenanthro-(3,4,5,6-bcdef)-ovalene (3) OMO-1 OMO LUMO LUMO+1

28 (4) OMO-1 OMO LUMO LUMO+1

29 (5) OMO-1 OMO LUMO LUMO+1

30 Figure S9: Total ground state electronic density of the investigated PAs 1-5. Strong polarization in the case of 2 led to higher chemical reactivity of the zigzag site compared to all other derivatives.