FRET in Orthogonally Arranged Chromophores. Supporting Information

Transcription

1 FRET in rthogonally Arranged Chromophores Heinz Langhals* a, Andreas Walter and Andreas J. Esterbauer a Eberhard Riedle* b and Igor Pugliesi b a Department of Chemistry, LMU University of Munich, Butenandtstraße 13, D Munich, Germany b Lehrstuhl für BioMoleculare ptik, LMU University of Munich, ettingenstrasse 67, D , Munich, Germany Supporting Information List of Contents 1. Experimental Section Page S2 1.1 General Page S2 1.2 Measurements of fluorescence quantum yields Page S2 2. Theoretical Section Page S3 2.1 Low frequency normal mode Page S3 2.2 Potential energy curves along the 20 cm -1 mode Page S4 2.3 Coulombic Coupling elements Page S5 2.4 Explanation of the linear fit model for the temperature dependence Page S6 3 Synthesis Page S4 *Authors to whom correspondence should be addressed. Heinz Langhals: Tel: +49 (0) Fax: +49 (0) address: Langhals@lrz.uni-muenchen.de Eberhard Riedle: Tel: +49 (0) Fax: +49 (0) address: Eberhard.Riedle@physik.uni-muenchen.de S1

2 1. Experimental Section 1.1 General IR spectra: Perkin Elmer 1420 Ratio Recording Infrared Spectrometer, FT 1000 UV/Vis spectra: Varian Cary 5000 and Bruins mega 20 fluorescence spectra: Varian Cary Eclipse MR spectroscopy: Varian Vnmrs 600 (600 MHz) mass spectrometry: Finnigan MAT was prepared according to the procedures outlined in ref S Measurements of fluorescence quantum yields Solutions of fluorescent dyes in chloroform were prepared in cuvettes with 1 cm path and with absorptivities of about 0.1 at the wavelength of fluorescence excitation. The absorptivity was thoroughly measured, the solution exactly diluted 1:10, the fluorescence spectrum recorded for 1 1 cm cuvettes and excitation by 90, corrected for the spectral response of the spectrometer and integrated. The same procedure was carried out for the reference. The weighed integrals were set into relation to give the final fluorescence quantum yields. The simple standard 2,9-bis-(1- hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone, R (S-13) was applied as the reference for routine measurements 1 and the broadband standard 2 2,10-bis(1-hexylheptyl)-6-[2-[3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1hpyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone, R (C25) for measurements with hypsochromic excitation, respectively, because of the more problematic calibration of the fluorescence spectrometer over a broad spectral range. S2

3 2. Theoretical Section 2.1 Low frequency normal mode Figure S1: 20 cm -1 butterfly mode used for the calculation of the FRET coupling strength. The atomic displacements are obtained from the normal mode analysis on the ground state structure of the perylene bisimide dyad 1 at the RI-BLYP/SVP/TZVP level of theory. S3

4 2.2 Potential energy curves along the 20 cm -1 mode The energy levels and electronic wavefunctions of the compound 1 were calculated with increasing deformation from the perpendicular equilibrium geometry along the butterfly normal mode shown in Figure S1. The TDDFT method with the 6-31G* basis set and the B3LYP functional was employed. Figure S2: Upper panel: Energies of the ground state and the lowest donor and acceptor states of compound 1 as a function of the bending coordinate q associated with the 20 cm -1 butterfly mode. Lower panel: energy splitting between the donor and acceptor excited states. S4

5 2.3 Coulombic Coupling elements Table S1: Electronic couplings V DA obtained from experiment and ab initio calculations of the equilibrium structure of the perylene bisimide dyad 1 and with the structure distorted along the 20 cm -1 butterfly mode shown in Figure S1. γ TDM is the deviation of the angle between the transition dipole moments localized on the two chromophores from 90. V DA (dd) is the dipole contribution to the Coulombic donor acceptor coupling (see equation (4)) and V DA (tot) includes all multipole orders. Expt (Chloro) τ FRET = 9.4 ps J DA = x 10-3 cm V DA = cm -1 q / Å γ TDM / V DA (dd) / cm -1 V DA (tot) / cm -1 CIS: TDDFT: S5

6 2.4 Explanation of the linear fit model for the temperature dependence As shown in equation (3) the FRET rate k FRET is proportional to the square of the electronic coupling V DA. If the coupling is expressed within the Förster approximation (i.e. only Coulombic contributions truncated at the dipole term), for a small deviation γ of the angle between the transition dipole moments from 90, V DA is proportional to cos(π-γ). We thus obtain equation (s1) ( ) DA cos sin k V π γ = γ γ (s1) FRET Due to the low frequency of the vibrations breaking the orthogonal arrangement between the transition dipole moments, the vibrational excitation is large enough for a classical treatment. We can therefore set the average vibrational energy E vib in the selected nondegenerate mode equal to the thermal energy kt. We thus obtain that the vibrational energy is related to the temperature and the angle γ as in equation (s2) 1 vib = = 2 force 2 E kt k γ (s2) where k force is the force constant of the harmonic oscillator. By combining equation (s1) and (s2), we therefore get equation (s3) 2 kfret Evib T γ (s3) which yields the linear relationship between k FRET and the temperature used to model the data shown in Figure 4. S6

7 3. Synthesis 4a 2,10-Bis(1-hexylheptyl)-6-[4 -[3,8,9,10-tetrahydro-9-(1-hexylheptyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]biphen-4-yl]-1h- pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)- hexone (4a): 2,10-Bis(1-hexylheptyl)-6-(4-iodophenyl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (2a, 150 mg, 143 µmol) and 2-(1- hexylheptyl)-9-(4-iodophenyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10-tetraone (3a, 111 mg, 143 mmol) were dissolved in anhydrous toluene (20 ml) under argon, heated to 70 C, treated with tetrabutylammonium bromide (81.0 mg, 251 µmol) and Pd(Ac) 2 (25.0 mg, 110 µmol), heated at 100 C, treated with Et 3 (1 ml), heated at 120 C for 15 h, treated with 2 M HCl (100 ml), extracted with chloroform, dried with magnesium sulphate and purified by column separation (silica gel, CHCl 3 /EtH = 60:1) and another column separation with fine silica (CHCl 3 /EtH = 90:1). Yield 34 mg (15 %) orange solid, m.p. > 250 C. R f value (CHCl 3 /EtH 60:1) = IR (ATR): ~ ν = (m), (m), (m), (w), (vs), (vs), (w), (s), (w), (m), (w), (w), (m), (s), (m), (s), (vs), (vs), (w), (m), (w), (w), (w), (w), (w), (w), (w), (w), (w), (w), (w), (w), (s), (w), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = (m, 18 H, 6 CH 3 ), (m, 48 H, 24 CH 2 ), S7

8 (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 1 H, -CH), (m, 2 H, 2 -CH), (m, 2 H, 2 CH aromat. ), (m, 4 H, 4 CH aromat. ), (m, 8 H, 8 CH perylene ), (m, 2 H, 2 CH aromat. ), (m, 4 H, 4 CH perylene ), ppm (m, 2 H, 2 CH perylene ). 13 C-MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.1, 22.6, 26.9, 29.3, 31.3, 32.4, 51.1, 54.8, 55.4, 122.0, 123.0, 123.4, 123.5, 125.0, 125.8, 126.7, 127.0, 128.0, 128.8, 131.9, 133.0, 134.2, 135.2, 135.3, 140.3, 163.4, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (37600), (21900), (44600), (75300), 490.3, (58600), nm (92400). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.50), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 437 nm, E 437 nm/1 cm = , reference 2,10-bis(1-hexylheptyl)-6-[2-[3,8,9,10- tetrahydro-9-(1-octylnonyl)-1,3,8,10-tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)- yl]ethyl]-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,6H,10H)-hexone R with Φ = 1.00): MS (FAB + ): m/z (%): 1570 (0.15) [M + ], 1569 (0.14) [M + +H], 1389 (0.14), 1207 (0.11), 1206 (0.09), 1024 (0.17). C 103 H (1569.8): Calcd. C 78.75, H 6.61, 4.46; found C 78.48, H 6.51, S8

9 4b 2,10-Bis(1-hexylheptyl)-6-[2 -[3,8,9,10-tetrahydro-9-(1-hexylheptyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]-5,5 -bipyrid-2-yl]-1h- pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)- hexone (4b): 2,10-Bis(1-hexylheptyl)-6-(5-iodopyridin-2-yl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (2b, 150 mg, 143 µmol) and 2-(1- hexylheptyl)-9-(5-iodopyridin-2-yl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10-tetraone (3b, 111 mg, 143 mmol), tetrabutylammonium bromide (81.0 mg, 251 µmol) and Pd(Ac) 2 (25.0 mg, 110 µmol) were allowed to react and purified as was described for dye 4a. Yield 22 mg (10 %) orange-red solid, m.p. > 250 C. R f value (CHCl 3 /EtH 60:1) = IR (ATR): ~ ν = (m), (vs), (m), (w), (s), (vs), (vs), (w), (s), (m), (w), (m), (w), (m), (s), (vs), (vs), (m), (s), (w), (w), (m), (m), (m), (m), (w), (w), (w), (vs), (s), (w), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = (m, 18 H, 6 CH 3 ), (m, 48 H, 24 CH 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 1 H, -CH), (m, 2 H, 2 -CH), 7.64 (d, 3 J(H,H) = 7.9 Hz, 1 H, CH aromat. ), 7.91 (d, 3 J(H,H) = 8.0 Hz, 1 H, CH aromat. ), 8.23 (dd, 3 J(H,H) = 7.9 Hz, 4 J(H,H) = 2.2 Hz, 1 H, CH aromat. ), 8.29 (dd, 3 J(H,H) = 8.0 Hz, 4 J(H,H) = 2.4 Hz, 1 H, CH aromat. ), (m, 8 H, 8 CH perylene ), (m, 4 H, 4 S9

10 CH perylene ), 9.38 (s, 1 H, CH aromat. ), 9.39 (s, 1 H, CH aromat. ), ppm (m, 2 H, 2 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 27.0, 29.2, 29.3, 29.7, 31.8, 31.9, 32.4, 54.8, 55.3, 122.2, 123.0, 123.2, 123.4, 124.2, 123.2, 126.4, 127.8, 128.4, 129.9, 131.9, 133.3, 134.2, 135.2,, 135.3, 137.1, 143.1, 146.0, 148.0, 148.5, 149.4, 163.4, ppm. UV/VIS (CHCl 3 ): λ max (E rel ) = (0.53), (0.18), (0.46), (0.80), (0.61), (1.00). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.50), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 437 nm, E 437 nm/1 cm = , reference 2,10-bis(1- hexylheptyl)-6-[2-[3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10-tetraoxoanthra[2,1,9-def:6,5,10- d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone R with Φ = 1.00): MS (FAB + ): m/z (%): 1572 (0.65) [M + ], 1571 (0.35) [M + H], 1391 (0.25), 1390 (0.23), 1209 (0.14), 1208 (13), 1026 (0.26), 925 (0.14). S10

11 7b 2,10-Bis(1-hexylheptyl)-6-[5-{2-[3,8,9,10-tetrahydro-9-(1-hexylheptyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]pyrid-5-yl}ethynypyrid-2-yl]- 1H-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2H,6H,10H)- hexone (7b): 2-(5-Ethynylpyridin-2-yl)-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10- tetraone (11b, 150 mg (223 µmol), 2,10-Bis(1-hexylheptyl)-6-(5-iodopyridin-2-yl)-1Hpyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2H,6H,10H)-hexone (2b, 281 mg, 268 µmol), Pd(PPh 3 ) 2 Cl 2 (11.2 mg, 16.0 µmol), PPh 3 (6.0 mg, 22.9 µmol) and CuI (4.0 mg, 21.0 µmol) were dissolved under argon in THF (16.6 ml), treated with Et 3 (8.3 ml), heated at 80 C for 16 h, quenched by the addition of 2 M aqueous HCl (100 ml), thoroughly extracted with chloroform, dried with magnesium sulphate and purified by column separation (silica gel, CHCl 3 /EtH 70:1). Yield 178 mg (50 %) orange solid, m.p. > 250 C. R f value (CHCl 3 /EtH = 60:1) = IR (ATR): ~ ν = (m), (vs), (m), (w), (w), (w), (vs), (vs), (w), (s), (w), (w), (m), (w), (w), (m), (vs), (vs), (vs), (w), (m), (w), (w), (w), (w), (w), (w), (w), (w), (m), (w), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = (m, 18 H, 6 CH 3 ), (m, 48 H, 24 CH 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 1 H, -CH), (m, 2 H, 2 -CH), 7.51 (d, 3 J(H,H) = 8.0 Hz, 1 H, CH aromat. ), S11

12 7.83 (d, 3 J(H,H) = 8.1 Hz, 1 H, CH aromat. ), 8.15 (dd, 3 J(H,H) = 7.9 Hz, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ), 8.29 (dd, 3 J(H,H) = 8.0 Hz, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ), (m, 8 H, 8 CH perylene ), (m, 4 H, 4 CH perylene ), 9.31 (s, 1 H, CH aromat. ), 9.33 (s, 1 H, CH aromat. ), ppm (m, 2 H, 2 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 27.0, 29.2, 29.7, 31.8, 32.4, 54.9, 55.3, 89.5, 89.7, 119.6, 120.2, 121.6, 122.8, 122.9, 123.0, 123.2, 123.9, 124.0, 125.0, 126.0, 126.5, 126.9, 127.6, 128.2, 129.3, 129.8, 131.8, 133.1, 135.0, 141.0, 141.1, 145.1, 148.6, 152.0, 152.4, 163.1, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (48500), (18900), (43900), (73500), 490.3, (56600), (90500). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.51), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 438 nm, E 438 nm/1 cm = , reference 2,10-bis(1-hexylheptyl)-6- [2-[3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10-tetraoxoanthra[2,1,9-def:6,5,10- d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone R with Φ = 1.00): MS (FAB + ): m/z (%): 1597 (0.55) [M + +H], 1596 (0.33) [M + ], 1416 (0.25), 1415 (0.25), 1233 (0.16), 1186 (0.33), 1051 (0.28), 822 (0.20). C 103 H (1595.8): Calcd. C 77.47, H 6.37, 6.14; found C 77.48, H 6.31, S12

13 8b 2,10-Bis(1-hexylheptyl)-6-[5-{2-[3,8,9,10-tetrahydro-9-(1-hexylheptyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]pyrid-5-yl}butadiynypyrid-2- yl]-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,6H,10H)-hexone (8b): 2,10-Bis(1-hexylheptyl)-6-(5-iodopyridin-2-yl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (2b, 271 mg, 258 µmol), 2-(5-buta-1,3- diynylpyridin-2-yl)-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10- tetraone (12b, 150 mg, 215 µmol), Pd(PPh 3 ) 2 Cl 2 (11.0 mg, 15.7 µmol), PPh 3 (6.0 mg, 22.9 µmol), CuI (4.1 mg, 21.5 µmol), Et 3 (8.0 ml), THF (16.0 ml), 2 M aqueous HCl (100 ml) were allowed to react as was described for dye 7b and purified by two column separations (silica gel, CHCl 3 /EtH 70:1 and silica gel, CHCl 3 /EtH 50:1). Yield 50 mg (29 %), m.p. > 250 C. R f value (CHCl 3 /EtH 40:1) = IR (ATR): ~ ν = (m), (vs), (m), (w), (s), (vs), (vs), (w), (s), (m), (w), (w), (w), (m), (w), (m), (m), (vs), (vs), (vs), (w), (m), (w), (w), (w), (w), (w), (w), (w), (w), (w), (s), (w), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = (m, 18 H, 6 CH 3 ), (m, 48 H, 24 CH 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 1 H, -CH), (m, 2 S13

14 H, 2 -CH), 7.47 (d, 3 J(H,H) = 8.1 Hz, 1 H, CH aromat. ), 7.87 (d, 3 J(H,H) = 8.0 Hz, 1 H, CH aromat. ), 8.11 (dd, 3 J(H,H) = 7.9 Hz, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ), 8.18 (dd, 3 J(H,H) = 8.0 Hz, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ), (m, 8 H, 8 CH perylene ), (m, 4 H, 4 CH perylene ), 9.19 (s, 1 H, CH aromat. ), 9.20 (s, 1 H, CH aromat. ), ppm (m, 2 H, 2 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.1, 22.6, 27.0, 27.1, 29.3, 31.8, 32.4, 54.9, 55.4, 77.6, 77.7, 78.9, 79.0, 118.7, 119.4, 121.6, 122.7, 122.8, 123.0, 123.9, 124.8, 125.9, 126.3, 126.7, 127.5, 127.9, 129.2, 129.7, 131.6, 132.9, 133.7, 134.9, 141.9, 145.3, 148.9, 152.9, 153.2, 162.9, ppm. UV/VIS (CHCl 3 ): λ max (E rel ) = (0.58), (0.20), (0.47), (0.80), (0.61), (1.00). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.51), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 436 nm, E 436 nm/1 cm = , reference 2,10-bis(1-hexylheptyl)-6-[2-[3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1hpyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone R with Φ = 1.00): MS (FAB + ): m/z (%): 1622 (1.10) [M + +H], 1621 (1.05) [M + ], 1440 (0.53), 1257 (0.40), 1075 (0.80), 664 (3.60), 648 (3.05). S14

15 8a 2,10-Bis(1-hexylheptyl)-6-[4-{4-[3,8,9,10-tetrahydro-9-(1-hexylheptyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]phenyl}butadiynylphenyl]-1h- pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)- hexone (8a): 2-(4-Bromoethynylphenyl)-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline- 1,3,8,10-tetraone (9, 36 mg, 48 µmol), 2,10-Bis(1-hexylheptyl)-6-(4-ethynylphenyl)-1Hpyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2H,6H,10H)-hexone (10, 50 mg, 53 mmol), CuI (1.0 mg, 5.3 µmol), PdCl 2 (PPh 3 ) 2 (4.0 mg, 5.7 µmol), THF (5 ml), diisopropylamine (2.5 ml) were allowed to react 3,4 as was described for dye 7b and purified by column separation (silica gel, CHCl 3 /EtH 100:1). Yield 34 mg (44%) orange solid, m.p. > 250 C. R f value (CHCl 3 /EtH 40:1) = IR (ATR): ~ ν = (s), (vs), (s), (w), (s), (vs), (w), (m), (m), (m), (w), (w), (m), (s), (s), (s), (m), (m), (w), (w), (w), (w), (w), (w), (w), (w), (m), (w), (w), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = (m, 18 H, 6 CH 3 ), (m, 48 H, 24 CH 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 1 H, - CH), (m, 2 H, 2 -CH), 7.23 (d, 3 J(H,H) = 7.7 Hz, 2 H, 2 CH aromat. ), (m, 4 H, 4 CH aromat. ), 7.78 (d, 3 J(H,H) = 7.7 Hz, 2 H, 2 CH aromat. ), (m, 8 H, 8 S15

16 CH perylene ), (m, 4 H, 4 CH perylene ), ppm (m, 2 H, 2 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.1, 22.7, 27.1, 29.3, 29.7, 31.9, 32.3, 54.9, 55.4, 74.8, 75.2, 81.0, 81.4, 121.8, 122.2, 122.3, 122.6, 123.0, 124.3, 125.2, 125.6, 126.4, 126.5, 127.1, 127.3, 128.7, 128.9, 129.2, 130.5, 131.4, 131.6, 132.5, 133.1, 133.3, 134.0, 135.4, 162.7, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (35700), (22100), (40700), (68200), (53500), nm (86500). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.50), nm (0.11). Fluorescence quantum yield (CHCl 3, λ exc = 436 nm, E 436 nm/1 cm = , reference 2,10-bis(1-hexylheptyl)-6-[2-[3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1hpyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone R with Φ = 1.00): MS (FAB + ) m/z (%): 1619 [M + +H] (0.11), 1618 [M + ] (0.11), 1437 (0.05), 1436 (0.05), 1255 (0.04), 1253 (0.04), 243 (8). C 107 H (1617.8): Calcd. C 79.38, H 6.41, 4.33; found 79.65, H 6.19, S16

17 7a 2,10-Bis(1-hexylheptyl)-6-[4-{4-[3,8,9,10-tetrahydro-9-(1-hexylheptyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]phenyl}ethynylphenyl]-1h- pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)- hexone (7a): 2,10-Bis(1-hexylheptyl)-6-(4-ethynylphenyl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (10, 100 mg, 106 µmol), 2-(1- hexylheptyl)-9-(4-iodophenyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10-tetraone (3a, 123 mg, 159 µmol), Pd(PPh 3 ) 2 Cl 2 (11 mg, 16 µmol), PPh 3 (4.0 mg, 15 µmol), CuI (3.0 mg, 16 µmol), anhydrous THF (10 ml), Et 3 (5 ml) were allowed to react as was described for dye 7b and purified by column separation (silica gel, CHCl 3 /EtH 80:1). Yield 61 mg (38 %) brownish orange solid, m.p. > 250 C. R f value (CHCl 3 /EtH 40:1) = IR (ATR): ~ ν = (m), (s), (m), (s), (vs), (m), (w), (m), (w), (m), (m), (m), (s), (vs), (m), (m), (w), (w), (w), (m), (w), (w), (w), (m), (w), (s), (s), cm -1 (m). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = (m, 18 H, 6 CH 3 ), (m, 48 H, 24 CH 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 1 H, -CH), (m, 2 H, 2 -CH), (m, 6 H, 6 CH aromat. ), (m, 8 S17

18 H, 8 CH perylene ), (m, 2 H, 2 CH aromat. ), (m, 4 H, 4 CH perylene ), ppm (m, 2 H, 2 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.1, 22.6, 27.0, 27.1, 29.3, 31.8, 32.4, 54.8, 55.4, 89.5, 90.5, 122.5, 122.6, 123.1, 123.2, 123.8, 126.5, 126.8, 128.8, 131.6, 132.5, 132.6, 134.3, 163.0, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (35800), (23000), (44000), (74100), (57500), nm (92300). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.50), nm (0.11).. Fluorescence quantum yield (CHCl 3, λ exc = 436 nm, E 436 nm/1 cm = , reference 2,10-bis(1-hexylheptyl)-6- [2-[3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10-tetraoxoanthra[2,1,9-def:6,5,10- d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone R with Φ = 1.00): MS (FAB + ): m/z (%): 1595 (0.075) [M + +H], 1594 (0.083) [M + ], 1413 (0.040), 1231 (0.030), 1230 (0.028), 1048 (0.075). C 105 H (1593.8): Calcd. C 79.07, H 6.51, 3.39; found C 78.89, H 6.45, S18

19 13 2,10-Bis(1-hexylheptyl)-6-{4-[4-(4-(3,8,9,10-tetrahydro-9-(1-hexylheptyl)-1,3,8,10- tetraoxoanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl)phenyl)bicyclo[2.2.2]oct-1- yl]phenyl}-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,6H,10H)-hexone (13): 2,10-Bis(1-hexylheptyl)furo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,10H)-hexone (12, 50 mg, 59 µmol) and 2-{4-[4-(4- aminophenyl)bicyclo[2.2.2]oct-1-yl]-phenyl}-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10- d'e'f']diisoquinoline-1,3,8,10-tetraone (11, 40 mg, 47 µmol) were dissolved in quinoline (6 ml), stirred at 150 C for 16 h, allowed to cool, precipitated with 2 m aqueous HCl, extracted with chloroform, dried with MgS4, purified by column separation (fine silica gel, chloroform/ethanol 40:1 and then chloroform/ethanol 50:1). Yield 15 mg (19 %) dark red solid, m.p. > 250 C. Rf (silica gel, CHCl3/EtH = 60:1) = IR (ATR): ~ ν = (vs), (s), (s), (s), (vs), (w), (m), (w), (m), (w), (w), (w), (w), (w), (s), (s), (w), (w), (w), (w), (w), (w), (w), (w), (w), (w), (w), (m), (w), (w), cm-1 (w). 1H MR (600 MHz, CDCl3, 25 C, TMS): δ = (m, 18 H, 6 CH3), (m, 48 H, 24 CH2), (m, 2 H, β- CH2), (m, 4 H, 2 β-ch2), 2.16 (s, 12 H, 6 CH2), (m, 2 H, β-ch2), (m, 4 H, 2 β-ch2), (m, 1 H, -CH), (m, 2 H, 2 -CH), 7.34 (d, 3J(H,H) = 8.3 Hz, 2 H, 2 CHaromat.), 7.62 (d, 3J(H,H) = 8.2 Hz, 2 H, 2 CHaromat.), (m, 4 H, 4 CHaromat.), (m, 8 H, 8 CHperylene), (m, 4 H, 4 CHperylene), ppm (m, 2 H, 2 CHperylene). 13C MR (150 MHz, CDCl3, 25 C, TMS): δ = 14.0, 22.6, 27.1, 29.3, 29.7, 31.8, 32.3, 32.9, 35.2, 35.3, 54.8, 55.3, 122.7, 123.3, 124.7, 126.4, 126.5, 126.7, 127.0, 127.4, 128.1, 128.7, 129.3, 129.5, 130.8, 131.6, 132.4, 132.8, S19

20 133.8, 134.6, 150.1, 150.2, 163.4, ppm. UV/VIS (CHCl3): λmax (ε) = (35000), (18600), (42500), (72400), (53100), nm (86200). Fluorescence (CHCl3): λmax (Irel) = (1.00), (0.50), nm (0.11). Fluorescence quantum yield (CHCl3, λexc = 437 nm, E437 nm/1 cm = , reference 2,10-bis(1-hexylheptyl)-6-[2- [3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10-tetraoxoanthra[2,1,9-def:6,5,10- d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone R with Φ = 1.00): Fluorescence quantum yield (CHCl3, λexc = 491 nm, E437 nm/1 cm = , reference 2,10- bis(1-hexylheptyl)-6-[2-[3,8,9,10-tetrahydro-9-(1-octylnonyl)-1,3,8,10-tetraoxoanthra[2,1,9- def:6,5,10-d'e'f']diisoquinolin-2(1h)-yl]ethyl]-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone R with Φ = 1.00): MS (FAB+): m/z (%): 1679 (0.04) [M++H], 1678 (0.04) [M+]. HRMS (C111H115510): Calcd [M++H], found , = E I λ in nm Figure S3. UV/Vis spectra in chloroform. Thick lines: Absorption (left) and fluorescence spectra of 13 (right). Thin lines: Absorption spectra of 14 (left) and 15 (middle) and fluorescence spectrum of 15 (right, nearly covered by the spectrum of 13). Insert: calculated structure (DFT B3-LYP) of the methyl analogue (R=CH 3 ) of 13. S20

21 I 3a 2-(1-Hexylheptyl)-9-(4-iodophenyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10- tetraone (3a): 9-(1-Hexylheptyl)-2-benzopyrano[6,5,4 :10,5,6]anthra[2,1,9-def]isoquinoline-1,3,8-10 tetraone (10, 1.00 g, 1.75 mmol) was stirred with imidazole (12 g) and the quantity of a micro spatulum of zinc acetate at 140 C until completely homogeneous, treated with 4-iodo aniline (495 mg, 2.26 mmol), stirred at 140 C for 3 h, allowed to cool to 50 C, treated with ethanol (50 ml), precipitated with acetic acid (80 ml) and 2 M aqueous HCl (80 ml), collected by vacuum filtration (D4 glass filter), dried in air and purified by column separation (silica gel, dichloromethane). Yield 1.05 g (78%) brightly red solid, m.p. > 250 C. R f value (silica gel, CH 2 Cl 2 ) = IR (ATR): ~ ν = (m), (s), (s), (vs), (vs), (s), (s), (w), (m), (w), (w), (m), (vs), (w), (s), (w), (w), (w), (w), (w), (w), (w), (w), (w), (w), (m), (w), cm -1 (w). 1 H-MR (600 MHz, CDCl 3, 25 C, TMS): δ = 0.83 (t, 3 J(H,H) = 7.0 Hz, 6 H, 2 CH 3 ), (m, 16 H, 8 CH 2 ), (m, 2 H, β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 1 H, -CH), 7.11 (d, 3 J(H,H) = 8.6 Hz, 2 H, 2 CH aromat. ), 7.90 (d, 3 J(H,H) = 8.6 Hz, 2 H, 2 CH aromat. ), ppm (m, 8 H, 8 CH perylene ). 13 C-MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 29.1, 31.7, 32.3, 54.8, 94.6, 123.1, 123.4, 126.4, 126.7, 129.5, 129.8, 130.6, 131.9, 135.3, 138.6, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (19400), (53100), nm (88000). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.52), nm (0.12). Fluorescence quantum yields (CHCl 3, λ exc = 488 nm, E 488 nm/1 cm = , reference 2,9-bis-(1-hexylheptyl)anthra[2,1,9- def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone R with Φ = 1.00): MS (DEP/EI): m/z (%): 775 (17) [M + +H], 774 (35) [M + ], 594 (21), 593 (69), 592 (100), 591 (10), 467 (11), 466 (18), 373 (11). C 43 H 39 I 2 4 (774.2): Calcd. C 66.67, H 5.07, 3.62; found C 66.51, H 4.87, S21

22 I 3b 2-(1-Hexylheptyl)-9-(5-iodopyridine-2-yl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline- 1,3,8,10-tetraone (3b): 9-(1-Hexylheptyl)-2-benzopyrano[6,5,4 :10,5,6]anthra[2,1,9-def]isoquinoline-1,3,8,10-tetraone (1.00 g, 1.75 mmol), 2-amino-5-iodopyridine (497 mg, 2.26 mmol), imidazole (18 g), ethanol (80 ml), and 2 M aqueous HCl (250 ml) were allowed to react and purified analogously to 2-(1- hexylheptyl)-9-(4-iodophenyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10-tetraone (3a) and further purified by column separation (silica gel, chloroform/ethanol 40:1). Yield 1.04 g (77 %) red solid, m.p. > 250 C. R f value (silica gel, CHCl 3 /EtH = 40:1) = IR (ATR): ~ ν = (m), (s), (m), (s), (vs), (s), (m), (w), (m), (w), (m), (vs), (s), (m), (w), (w), (w), (w), (w), (w), (s), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = 0.83 (t, 3 J(H,H) = 7.0 Hz, 6 H, 2 CH 3 ), (m, 16 H, 8 CH 2 ), (m, 2 H, β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 1 H, - CH), 7.27 (d, 3 J(H,H) = 7.1 Hz, 1 H, CH aromat. ), 8.27 (dd, 3 J(H,H) = 8.2 Hz, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ), (m, 8 H, 8 CH perylene ), 8.96 ppm (d, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ). 13 C-MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 26.9, 29.2, 31.8, 32.3, 54.8, 93.7, 122.9, 123.0, 123.4, 125.9, 126.4, 126.7, 129.5, 130.0, 131.8, 134.1, 135.4, 146.9, 148.4, 156.3, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (20300), (56100), nm (93800). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.51), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 490 nm, E 490 nm/1 cm = , reference 2,9-bis-(1- hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone R with Φ = 1.00): MS (DEP/EI): m/z (%): (14) [M + +H], (31) [M + ], (20), (66), (100), (13), (10), (11), (11), (30), (34), (15). HRMS (C 42 H I): Calcd , found , = C 42 H 38 I 3 4 (775.2): Calcd. C 65.03, H 4.94, 5.42; found C 65.33, H 5.03, S22

23 I 2a d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (2a): 2,10-Bis(1-hexylheptyl)-6-(4-iodophenyl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-2,10-Bis(1-hexylheptyl)furo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,10H)-hexone (12, 1.00 g, 1.18 mmol), dicyclohexylcarbodiimide (DCC, 1.22 g, 5.90 mmol) and 4-iodo aniline (1.29 g, 5.90 mmol) were dissolved at room temperature, in a small amount of chloroform (20 ml), treated with trifluoroacetic acid (10 drops), stirred (95 C, 18 h), treated with water (100 ml) and separated from the aqueous phase. The latter was extracted with chloroform (100 ml) and the combined organic phases were dried with magnesium sulphate, evaporated and purified by column separation (silica gel, toluene). Yield 870 mg (70 %) orange solid, m.p. > 250 C. R f value (silica gel, toluene) = IR (ATR): ~ ν = (m), (s), (m), (w), (vs), (vs), (m), (m), (w), (s), (m), (m), (m), (vs), (vs), (m), (s), (m), (m), (m), (s), (m), (w), (m), (w), (w), (w), (w), (w), (vs), (m), (m), (m), (m), (w), (w), (m), cm -1 (w). 1 H-MR (600 MHz, CDCl 3, 25 C, TMS): δ = 0.84 (t, 3 J(H,H) = 7.0 Hz, 12 H, 4 CH 3 ), (m, 32 H, 16 CH 2 ), (m, 4 H, 2 β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, 2 - CH), 7.54 (d, 3 J(H,H) = 8.4 Hz, 2 H, 2 CH aromat. ), 8.00 (d, 3 J(H,H) = 8.5 Hz, 2 H, 2 CH aromat. ), (m, 4 H, 4 CH perylene ), ppm (m, 2 H, 2 CH perylene ). 13 C-MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 27.0, 29.3, 31.8, 32.5, 55.4, 93.8, 122.8, 123.8, 126.6, 127.4, 128.3, 131.1, 138.5, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (41100), (18300), S23

24 (39400), nm (60300). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), nm (0.86). Fluorescence quantum yield (CHCl 3, λ exc = 435 nm, E 435 nm/1 cm = , reference 2,9-bis-(1- hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone R with Φ = 1.00): MS (DEP/EI): m/z (%): (26) [M + +H], (41) [M + ], (42), (76), (36), (31), (56), (100), (90), (59), (47), (26). HRMS (C 60 H I): Calcd ; found , = C 60 H I (1049.4): Calcd. C 68.63, H 6.14, 4.00; found C 68.73, H 6.03, S24

25 I 2b 6-(5-Iodopyridine-2-yl)-2,10-bis(1-hexylheptyl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10- def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (2b): 2,10-Bis(1-hexylheptyl)furo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,10H)-hexone (12, 600 mg, 707 µmol), 2-amino-5-iodopyridine (777 mg, 3.54 mmol), DCC (732 mg, 3.54 mmol), trifluoacetic acid (6 drops), and chloroform (15 ml) were allowed to react analogously to 6-(4-iodophenyl)-2,10-bis(1-hexylheptyl)-1Hpyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2H,6H,10H)-hexone (2a) and purified by column separation (silica gel, toluene). Yield 390 mg (53%) yellow solid. Alternatively, 2,10-bis(1-hexylheptyl)furo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,10H)-hexone (600 mg, 707 µmol), 2-amino-5-iodopyridine (777 mg, 3.54 mmol) and quinoline (30 ml) were allowed to react at 150 C for 16 h and purified analogously to 6-(4- iodophenyl)-2,10-bis(1-hexylheptyl)-1h-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (2a) and purified by column separation (silica gel, toluene). Yield 390 mg (64%) yellow solid, m.p. > 250 C. R f value (toluene) = IR (ATR): ~ ν = (m), (s), (m), (w), (vs), (vs), (w), (m), (w), (w), (m), (m), (vs), (vs), (w), (w), (w), (w), (w), (w), (w), (w), (s), (w), (m), (w), cm -1 (w). 1 H-MR (600 MHz, CDCl 3, 25 C, TMS): δ = 0.82 (t, 3 J(H,H) = 7.1 Hz, 12 H, 4 CH 3 ), (m, 32 H, 16 CH 2 ), (m, 4 H, 2 β-ch 2 ), (m, 4 H, 2 β-ch 2 ), (m, 2 H, 2 -CH), 7.71 (d, 3 J(H,H) = 8.4 Hz, 1 H, CH aromat. ), 8.39 (dd, 3 J(H,H) = 6.0 Hz, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ), 8.98 (d, 4 J(H,H) = 2.0 Hz, 1 H, CH aromat. ), (m, 4 H, 4 CH perylene ), ppm S25

26 (m, 2 H, 2 CH perylene ). 13 C-MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 27.0, 29.3, 31.8, 32.4, 55.3, 92.9, 123.0, 123.9, 124.0, 124.7, 126.7, 127.6, 127.8, 132.9, 144.9, 146.9, 155.8, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (49300), (16400), (41000), nm (63900). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), nm (0.76). Fluorescence quantum yield (CHCl 3, λ exc = 437 nm, E 437 nm/1 cm = 0.140, reference 2,9-bis-(1-hexylheptyl)anthra[2,1,9- def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone with Φ = 1.00): MS (DEP/EI): m/z (%): (10) [M + +H], (14) [M + ], (13), (30), (22), (31), (57), (23), (/29), (56), (25), (100), 69.0 (71). C 59 H I (1050.4): Calcd. C 67.42, H 6.04, 5.33; found C 67.31, H 5.99, S26

27 Br 9 1,3,8,10-tetraone (9): 2-(4-Bromoethynylphenyl)-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline- 2-(4-Ethynylphenyl)-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10- tetraone (11a, 300 mg, 439 µmol) was dissolved in dichloromethane (40 ml) and treated 5 under argon with tetrabromomethane (2.33 g, 7.02 mmol) and slowly with triphenylphosphane (3.69 g, 14.1 mmol), stirred at room temperature for 15 h, evaporated and purified by column separation (silica gel, chloroform/ethanol 100:1). Yield 42 mg (13 %) brightly red shining solid, m.p. > 250 C. R f value (CHCl 3 /EtH = 80:1) = IR (ATR): ~ ν = (m), (m), (m), (s), (vs), (s), (m), (w), (w), (w), (m), (vs), (s), (w), (m), (w), (w), (w), (w), (w), (m), (w), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = 0.83 (t, 3 J(H,H) = 6.9 Hz, 6 H, 2 CH 3 ), (m, 16 H, 8 CH 2 ), (m, 2 H, β- CH 2 ), (m, 2 H, β-ch 2 ), (m, 1 H, -CH), 7.33 (d, 3 J H,H = 8.5 Hz, 2 H, 2 CH aromat. ), 7.64 (d, 3 J H,H = 8.5 Hz, 2 H, 2 CH aromat. ), ppm (m, 8 H, 8 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 26.9, 29.2, 31.7, 32.4, 51.1, 54.8, 79.4, 123.0, 123.4, 123.5, 126.4, 126.7, 128.8, 129.5, 129.9, 131.9, 133.0, 134.2, 135.2, 135.3, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (18100), (49500), nm (82400). Fluorescence (CHCl 3 ): λ max (I rel. ) = (1.00), (0.50), (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 490 nm, E 490 nm/1 cm = , reference 2,9-bis-(1-hexylheptyl)anthra[2,1,9- def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone R with Φ = 1.00): MS (FAB + ): m/z (%): 751 (30) [M + +H], 750 (12) [M + ], 569 (100), 553 (20), 491 (30), 373 (80). C 45 H 39 Br 2 4 (750.2): Calcd. C 71.90, H 5.23, 3.73; found C 71.57, H 5.29, S27

28 10 6-(4-Ethynylphenyl)-2,10-bis(1-hexylheptyl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10-def:7,8,9- d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (10): 2,10-Bis(1-hexylheptyl)furo[3',4':4,5]pyreno[2,1,10-def:7,8,9-d'e'f']diisoquinoline- 1,3,5,7,9,11(2H,10H)-hexone (12, 1.30 g, 1.53 mmol), 4-ethynylaniline (900 mg, 7.68 mmol), DCC (1.59 g, 7.68 mmol), TFA (13 drops) and dry chloroform (36 ml) were allowed to react analogously to 6-(4-iodophenyl)-2,10-bis(1-hexylheptyl)-1H-pyrrolo[3',4':4,5]pyreno[2,1,10- def:7,8,9-d'e'f']diisoquinoline-1,3,5,7,9,11(2h,6h,10h)-hexone (2a) and purified by column separation (silica gel, toluene). Yield 1.12 g (77 %), m.p. > 250 C. R f value (silica gel, toluene) = IR (ATR): ~ ν = (m), (s), (m), (w), (vs), (vs), (m), (m), (w), (s), (m), (m), (m), (vs), (vs), (m), (s), (m), (m), (m), (s), (m), (w), (m), (w), (w), (w), (w), (w), (vs), (m), (m), (m), (m), (w), (w), (m), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C, TMS): δ = 0.83 (t, 3 J(H,H) = 6.9 Hz, 12 H, 4 CH 3 ), (m, 32 H, 16 CH 2 ), (m, 4 H, 2 β-ch 2 ), (m, 4 H, 2 β-ch 2 ), 3.21 (s, 1 H, CH alkinyl. ), (m, 2 H, 2 -CH), (m, 4 H, 4 CH aromat. ), (m, 4 H, 4 CH perylene ), ppm (m, 2 H, 2 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C, TMS): δ = 14.0, 22.6, 27.1, 29.3, 29.7, 31.8, 32.4, 55.4, 78.4, 82.9, 122.2, 123.0, 123.9, 124.7, 126.4, 126.8, 127.6, 131.6, 133.0, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (40400), (18300), (41200), nm (63500). Fluorescence (CHCl 3 ): λ max (I) = (1.00), nm (0.86). Fluorescenece quantum yield (CHCl 3, λ exc = 435 nm, E 435 nm/1 cm = S28

29 0.0089, reference 2,9-bis-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline- 1,3,8,10(2H,9H)-tetraone R with Φ = 1.00): MS (DEP/EI): m/z (%): (3) [M + ], (5), (6), (5), (9), (9), (6), (25), (16), 98.1 (14), 97.1 (36), 83.1 (56), 70.1 (55), 69.1 (100). HRMS (C 62 H ): calcd ; found , = , C 62 H (947.5): Calcd. C 78.53, H 6.91, 4.43; found C 78.85, H 6.90, S29

30 TMS 5a 2-(1-Hexylheptyl)-9-(4-trimethylsilanylethynylphenyl)anthra[2,1,9-def;6,5,10- d'e'f']diisoquinoline-1,3,8,10-tetraone (5a): 2-(1-Hexylheptyl)-9-(4-iodophenyl)anthra[2,1,9-def;6,5,10-d'e'f']-diisochinolin-1,3,8,10-tetraon (3a, 300 mg, 387 µmol), ethynyltrimethylsilane (1.09 ml, 7.74 mmol), triphenylphosphane (12 mg, 46 µmol), Pd(PPh 3 ) 2 Cl 2 (46 mg, 66 µmol) and CuI (9.0 mg, 47 µmol) were dissolved in anhydrous THF (15 ml) under argon, treated dropwise with triethylamine (7.5 ml), stirred for 16 h, treated with 2 M HCl, extracted with chloroform, dried with MgS 4 and purified by column separation (silica gel, CHCl 3 /EtH = 60:1). Yield 273 mg (95 %) brightly red solid, m.p. > 250 C. R f value (silica gel, CHCl 3 /EtH 60:1) = IR (ATR): ~ ν = (w), (m), (m), (m), (w), (w), (w), (s) (s), (vs), (s), (m), (m), (w), (w), (m), (vs), (w), (s), (w), (w), (m), (w), (w), (w), (w), (w), (m), (m), (m), (m), (m), (w), (m), (w), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C): δ = 0.27 (s, 9 H, Si(CH 3 ) 3 ), 0.82 (t, 3 J(H,H) = 7.2 Hz, 6 H, 2 CH 3 ), (m, 16 H, 8 CH 2 ), (m, 2 H, β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 1 H, -CH), 7.30 (d, 3 J(H,H) = 8.6 Hz, 2 H, 2 CH aromat. ), 7.65 (d, 3 J(H,H) = 8.1 Hz, 2 H, 2 CH aromat. ), ppm (m, 8 H, 8 CH perylene ). 13 C MR (150 MHz, CDCl 3, 25 C): δ = 0.1, 14.1, 22.6, 27.0, 29.3, 31.8, 32.4, 54.9, 95.5, 104.4, 123.0, 123.1, 123.3, 124.0, 124.2, 126.3, 126.6, 128.7, 129.5, 129.8, 131.1, 131.8, 133.0, 134.1, 135.0, 135.1, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (19100), (52600), nm (87500). Fluorescence (CHCl 3 ) : λ max (I rel. ) = (1.00), (0.50), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 488 nm, E 488 nm/1 cm = , reference 2,9-bis-(1- hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone R with Φ = 1.00): MS (DEP/EI) m/z (%): (14) [M + +2H], (40) [M + +H], (79) [M + ], (11), (41), (87), (90), (15) (47), (100), (21), (34), (15), 83.0 (13), 44.0 (28). HRMS (C 48 H Si): Calcd. S30

31 ; found , = C 48 H Si (744.3): Calcd C 77.39, H 6.49, 3.76; found C 77.23, H 6.45, S31

32 11a 2-(4-Ethynylphenyl)-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10- tetraone (11a): 2-(1-Hexylheptyl)-9-(4-trimethylsilanylethynylphenyl)anthra[2,1,9-def;6,5,10- d'e'f']diisoquinoline-1,3,8,10-tetraone (5a, 300 mg, 403 µmol) was dissolved in THF (27 ml) treated with a solution of Bu 4 F (0.81 ml, 0.81 mmol, 1 M in THF), stirred at room temperature for 10 min, treated with water (100 ml, extracted with chloroform (3 x 100 ml), dried with MgS 4 and purified by column separation (silica gel, CHCl 3 /EtH 100:1). Yield 195 mg (72 %) brightly red solid m.p. 250 C. R f value (silica gel, CHCl 3 /EtH 60:1) = H MR (400 MHz, CDCl 3, 25 C): δ = 0.82 (t, 3 J(H,H) = 6.9 Hz, 6 H, 2 CH 3 ), (m, 16 H, 8 CH 2 ), (m, 2 H, β-ch 2 ), (m, 2 H, β-ch 2 ), 3.15 (s, 1 H, CH alkynyl. ), (m, 1 H, -CH), 7.33 (d, 3 J(H,H) = 8.6 Hz, 2 H, 2 CH aromat. ), 7.69 (d, 3 J(H,H) = 8.4 Hz, 2 H, 2 CH aromat. ), ppm (m, 8 H, 8 CH perylene ). 13 C MR (100 MHz, CDCl 3, 25 C): δ = 14.1, 22.6, 27.0, 29.2, 31.8, 32.4, 54.9, 77.2, 78.2, 82.9, 122.9, 123.0, 123.3, 126.3, 126.6, 128.8, 129.4, 129.7, 131.8, 133.2, 134.1, 135.2, 135.3, ppm. UV/Vis (CHCl 3 ): λ max (ε) = (19300), (51800), (84600). MS (DEP/EI) m/z (%): (13) [M + ], (17), (32), (41), (10), (7), (10), (10), 84.9 (10), 82.9 (11), 69.1 (9), 69.0 (11), 55.0 (11), 44.0 (100). HRMS (C 45 H ): Calcd ; found , = C 45 H (672.3): Calcd. C 80.33, H 5.99, 4.16; found C 80.45, H 5.94, S32

33 TMS 5b 2-(1-Hexylheptyl)-9-(5-trimethylsilanylethynylpyridin-2-yl)anthra[2,1,9-def;6,5,10- d'e'f']diisochinolin-1,3,8,10-tetraone (5b): 2-(1-Hexylheptyl)-9-(5-iodopyridin-2- yl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10-tetraone (3b, 320 mg, 413 µmol), ethynyltrimethylsilane (1.16 ml, 8.25 mmol), triphenylphosphane (11 mg, 42 µmol) ; Pd(PPh 3 ) 2 Cl 2 (21 mg, 30 µmol), CuI (8.0 mg, 42 µmol), THF (16 ml) and triethylamine (7 ml) were allowed to react as was described for 5a and purified by column separation (silica gel, CHCl 3 /EtH 50:1). Yield 276 mg (90 %) red solid, m.p. > 250 C. R f value (silica gel, CHCl 3- /EtH 40:1) = IR (ATR): ~ ν = (m), (s), (m), (w), (s) (vs), (vs), (m), (w), (w), (w), (m), (w), (vs), (w), (s), (w), (m), (w), (w), (w), (w), (m), (m), (m), (w), (m), cm -1 (w). 1 H MR (600 MHz, CDCl 3, 25 C): δ = 0.29 (s, 9 H, Si(CH 3 ) 3 ), 0.82 (t, 3 J(H,H) = 7.0 Hz, 6 H, 2 CH 3 ), (m, 16 H, 8 CH 2 ), (m, 2 H, β-ch 2 ), (m, 2 H, β-ch 2 ), (m, 1 H, -CH), 7.39 (d, 3 J(H,H) = 8.1 Hz, 1 H, CH aromat. ), 7.98 (dd, 3 J(H,H) = 8.1 Hz, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ), (m, 8 H, 8 CH perylene ), 8.78 ppm (d, 4 J(H,H) = 2.3 Hz, 1 H, CH aromat. ). 13 C MR (150 MHz, CDCl 3, 25 C): δ = 0.2, 14.0, 22.6, 26.9, 29.2, 31.7, 32.3, 54.8, 99.7, 100.6, 121.1, 123.0, 123.4, 123.6, 126.3, 126.7, 129.5, 129.9, 131.8, 134.2, 135.3, 141.3, 148.0, 152.8, ppm. UV/VIS (CHCl 3 ): λ max (E) = (0.22), (0.60), nm (1.00). Fluorescence (CHCl 3 ): λ max (I rel ) = (1.00), (0.51), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 490 nm, E 490 nm/1 cm = , reference 2,9-bis-(1- hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2h,9h)-tetraone R with Φ = 1.00): MS (DEP/EI) m/z (%): (14) [M + +H], (36) [M + ], (26), (63), (78), (17) (29), (23),, (21), (42), 71.0 (20), 69.1 (31), 57.1 (30), 55.0 (38), 44.1 (100). HRMS (C 47 H Si): Calcd , found , = S33

34 11b 2-(5-Ethynylpyridin-2-yl)-9-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline- 1,3,8,10-tetraone (11b): 2-(1-Hexylheptyl)-9-(5-trimethylsilanylethynylpyridin-2- yl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10-tetraone (5b, 240 mg, 321 µmol) was dissolved in THF (21 ml), treated with Bu 4 F solution (0.71 ml, 0.71 mmol, 1 M in THF), stirred at room temperature for 30 seconds, treated with distilled water (100 ml), extracted with chloroform (3 100 ml), dried with magnesium sulphate and purified by column separation (silica gel, CHCl 3 /EtH 50:1). Yield 212 mg (95 %) red solid, m.p. > 250 C. R f value (silica gel, CHCl 3 /EtH 40:1) = IR (ATR): ~ ν = (w), (w), (m), (m), (m), (w), (w), (w), (m), (s) (vs), (w), (s), (m), (m), (w), (w), (m), (vs), (vs), (w), (m), (m), (w), (w), (w), (w), (w), (w), (m), (w), cm -1 (m). 1 H MR (600 MHz, CDCl 3, 25 C): δ = 0.82 (t, 3 J(H,H) = 7.1 Hz, 6 H, 2 CH 3 ), (m, 16 H, 8 CH 2 ), (m, 2 H, β-ch 2 ), (m, 2 H, β-ch 2 ), 3.31 (s, 1 H, CH alkynylic. ), (m, 1 H, -CH), 7.42 (d, 3 J(H,H) = 8.1 Hz, 1 H, CH aromat. ), 8.03 (d, 3 J(H,H) = 8.0 Hz, 1 H, CH aromat. ), (m, 8 H, 8 CH perylene ), 8.83 ppm (s, 1 H, CH aromat. ). 13 C MR (150 MHz, CDCl 3, 25 C): δ = 14.0, 22.6, 26.9, 29.2, 31.7, 32.3, 54.8, 79.6, 81.8, 120.1, 123.0, 123.1, 123.4, 123.7, 126.4, 126.8, 129.5, 130.0, 131.9, 134.2, 135.5, 141.6, 148.6, 153.0, ppm. UV/VIS (CHCl 3 ): λ max (ε) = (19100), (50300), nm (82700). Fluorescence (CHCl 3 ) : λ max (I rel ) = (1.00), (0.51), nm (0.12). Fluorescence quantum yield (CHCl 3, λ exc = 490 nm, E 490 nm/1 cm = , reference 2,9-bis-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone R with Φ = 1.00): MS (DEP/EI) m/z (%): (12) [M + +H], (21) [M + ], (14), (13), (33), (44), (73), (14), (21), (65), (100), (23), 69.1 (26), 55.1 (28), 44.0 (25). HRMS (C 44 H Si): Calcd , found , = C 44 H Si (673.3): Calcd. C 78.43, H 5.83, 6.24; found C 77.97, H 5.84, S34