Supporting Information

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1 Supporting Information Intramolecular Charge-Transfer Interaction of Donor Acceptor Donor Arrays Based on Anthracene Bisimide Tetsuo Iwanaga, *, Marina Ogawa, Tomokazu Yamauchi, and Shinji Toyota *, Department of Chemistry, Faculty of Science, Okayama University of Science, 1 1 Ridaicho, Kita-ku, Okayama , Japan. Department of Chemistry and Materials Science, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo , Japan. iwanaga@chem.ous.ac.jp, stoyota@cms.titech.ac.jp Contents General S2 DFT Calculation S3-S16 Cyclic Voltammograms S17 Electronic Spectra S18 References S19 1 H and 13 C NMR Spectra of D2, D1, A2 and A1 S20-S23 S1

2 General. Melting points are uncorrected. NMR spectra were measured on a 400 spectrometer ( 1 H: 400 MHz, 13 C: 100 MHz). High-resolution mass spectra were measured by the FAB method (double-focusing magnetic sector analyzer). The FAB-MS spectra were recorded with m-nitrobenzyl alcohol as a matrix. UV spectra were measured with a 10 mm cell. IR spectra were measured as KBr pellets. Fluorescence spectra were measured with a 10 mm cell with a sample degassed by Ar gas immediately before measurements. Absolute quantum yields determined by a calibrated integrating sphere system in chloroform.. The fluorescence lifetimes were measured on a Spectra-Physics time-resolved spectrofluorometer system with a Ti:Sapphire laser. Cyclic voltammograms were performed using a cell equipped with a glassy carbon as working electrode, a platinum as the counter electrode, Ag/Ag + as the reference electrode, and 0.1 M n-bu 4 NClO 4 as the supporting electrolyte. Column chromatography was carried out with Silica Gel 60N ( mesh). S2

3 DFT Calculation. The calculations were carried out with Gaussian 09W programs1 on a Windows computer. These structures were optimized by the hybrid DFT method at the B3LYP/6-31G(d) level. The frequency analysis was carried out for the global minimum structures of the all compounds, giving no imaginary frequency. The calculation of excited states of D1, D2, A1, and A2 (octyl groups were replaced by methyl groups) were performed by the TD-DFT method at the B3LYP/6-31G(d) level of theory to afford the excitation energies, oscillator strengths, transition velocity dipole moment, and transition magnetic dipole moments for the lowest 20 excited states. Each excitation was treated as a Gaussian-type function with a half bandwidth of 1500 cm 1. A1' D1' HOMO LUMO Figure S1. MO plots of calculated structure of D1 and A1 (N-Me) using the B3LYP/6-31G(d) level of theory. S3

4 D2' D1' Side Top Figure S2. Optimized structures of D2 and D1 (N-Me) at B3LYP/6-31G(d) level. Oxygen atoms and nitrogen atoms are shown in red and blue color, respectively. A2' A1' Side Top Figure S3. Optimized structures of A2 and A1 (N-Me) at B3LYP/6-31G(d) level. Oxygen atoms and nitrogen atoms are shown in red and blue color, respectively. S4

5 Table S1. Coordinates of D2 at B3LYP/6-31G(d) level. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S5

6 S6

7 Sum of electronic and zero-point Energies = (a.u.) S7

8 Table S2. Coordinates of D1 at B3LYP/6-31G(d) level. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S8

9 S9

10 Sum of electronic and zero-point Energies = (a.u.) Table S3. Coordinates of A2 at B3LYP/6-31G(d) level. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S10

11 S11

12 S12

13 Sum of electronic and zero-point Energies = (a.u.) Table S4. Coordinates of A1 at B3LYP/6-31G(d) level. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S13

14 S14

15 S15

16 Sum of electronic and zero-point Energies = (a.u.) S16

17 Cyclic Voltammograms. Cyclic voltammetry was performed by using a cell equipped with a glassy carbon as working electrode, a platinum wire as counter electrodes, and Ag/AgNO 3 as a referential electrode. All electrochemical measurements were performed in dichloromethane solution (1.0 mmol L 1 ) containing 0.10 mol L 1 tetrabutylammonium perchlorate at room temperature. D2 Oxidation Reduction D1 Potential /V vs. Fc/Fc + Potential /V vs. Fc/Fc + A2 Potential /V vs. Fc/Fc + Potential /V vs. Fc/Fc + A1 Potential /V vs. Fc/Fc + Potential /V vs. Fc/Fc + Potential /V vs. Fc/Fc + Potential /V vs. Fc/Fc + Figure S4. Cyclic voltammograms of ABI derivatives in CH 2 Cl 2 with 0.1 M n-bu 4 NClO 4 as supporting electrolyte, Ag/Ag + as reference electrode, glass carbon disk as working electrode, Pt wire as counter electrode, and scan rate at 0.1 V s -1. S17

18 Electronic Spectra Table S5. Photophysical Data of ABI derivatives. Compd Absorption (/nm) Emission (/nm) Benzene CHCl 3 THF Benzene CHCl 3 THF D2 499 a 479 a b c D1 490 a 427 a b c A b 641 b A b 580 b a) Shoulder band. b) Weak fluorescence. c) Not measured due to weak fluorescence. Absorption Emission THF A2# ε /10 4 L mol -1 cm D2# D1# A2# A1# Normalized Intensity A1# Wavelength /nm Wavelength /nm Benzene ε /10 4 L mol -1 cm D2# D1# A2# A1# Normalized Intensity D2# D1# A2# A1# Wavelength /nm Wavelength /nm Figure S5. Electronic spectra of ABI derivatives in THF (top) and benzene (bottom). S18

19 References S1. Gaussian 09, Revision C.01, 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.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, 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, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, S19

20 abundance PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 0.2[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm auto_reference( 5[%], TRUE ) X : parts per Million : Proton abundance PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 2.0[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm Filename = 2Ph2NPh-ABI02 cm-13c-2-3. Author = delta Experiment = single_pulse_dec.jxp Sample_Id = 2Ph2NPh-ABI02 Solvent = CHLOROFORM-D Creation_Time = 4-FEB :31:30 Revision_Time = 5-FEB :22:53 Current_Time = 30-MAR :27:58 Data_Format = 1D COMPLEX Dim_Size = Dim_Title = Carbon13 Dim_Units = [ppm] Dimensions = X Site = ECS 400 Spectrometer = DELTA2_NMR Field_Strength = [T] (400[MHz]) X_Acq_Duration = [s] X_Domain = 13C X_Freq = [MHz] X_Offset = 100[ppm] X_Points = X_Prescans = 4 X_Resolution = [Hz] X_Sweep = [kHz] X_Sweep_Clipped = [kHz] Irr_Domain = Proton Irr_Freq = [MHz] Irr_Offset = 5[ppm] Clipped = TRUE Scans = Total_Scans = Relaxation_Delay = 2[s] Recvr_Gain = 60 Temp_Get = 18.9[dC] X_90_Width = 10.8[us] X_Acq_Time = [s] X_Angle = 30[deg] X_Atn = 8.2[dB] X_Pulse = 3.6[us] Irr_Atn_Dec = 22.03[dB] Irr_Atn_Noe = 22.03[dB] Irr_Noise = WALTZ Irr_Pwidth = 0.115[ms] Decoupling = TRUE Initial_Wait = 1[s] Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : Carbon Figure S6. 1 H NMR (400 MHz: top) and 13 C NMR (100 MHz: bottom) of D2 in CDCl S20

21 abundance PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 0.2[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm auto_reference( 5[%], TRUE ) X : parts per Million : Proton abundance PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 2.0[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm Filename = Ph2NPh-ABI01 cm-13c-1-3.j Author = delta Experiment = single_pulse_dec.jxp Sample_Id = Ph2NPh-ABI01 Solvent = CHLOROFORM-D Creation_Time = 4-FEB :52:31 Revision_Time = 4-FEB :03:33 Current_Time = 30-MAR :31:34 Data_Format = 1D COMPLEX Dim_Size = Dim_Title = Carbon13 Dim_Units = [ppm] Dimensions = X Site = ECS 400 Spectrometer = DELTA2_NMR Field_Strength = [T] (400[MHz]) X_Acq_Duration = [s] X_Domain = 13C X_Freq = [MHz] X_Offset = 100[ppm] X_Points = X_Prescans = 4 X_Resolution = [Hz] X_Sweep = [kHz] X_Sweep_Clipped = [kHz] Irr_Domain = Proton Irr_Freq = [MHz] Irr_Offset = 5[ppm] Clipped = TRUE Scans = 811 Total_Scans = 811 Relaxation_Delay = 2[s] Recvr_Gain = 60 Temp_Get = 19.3[dC] X_90_Width = 10.8[us] X_Acq_Time = [s] X_Angle = 30[deg] X_Atn = 8.2[dB] X_Pulse = 3.6[us] Irr_Atn_Dec = 22.03[dB] Irr_Atn_Noe = 22.03[dB] Irr_Noise = WALTZ Irr_Pwidth = 0.115[ms] Decoupling = TRUE Initial_Wait = 1[s] Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : Carbon Figure S7. 1 H NMR (400 MHz: top) and 13 C NMR (100 MHz: bottom) of D1 in CDCl S21

22 abundance PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 0.2[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm auto_reference( 5[%], TRUE ) X : parts per Million : Proton (thousandths) PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 2.0[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm Filename = DiPh2NPhYneABI cm-13c-4-7 Author = delta Experiment = single_pulse_dec.jxp Sample_Id = DiPh2NPhYneABI Solvent = CHLOROFORM-D Creation_Time = 11-DEC :44:32 Revision_Time = 12-DEC :51:23 Current_Time = 30-MAR :21:19 Data_Format = 1D COMPLEX Dim_Size = Dim_Title = Carbon13 Dim_Units = [ppm] Dimensions = X Site = ECS 400 Spectrometer = DELTA2_NMR Field_Strength = [T] (400[MHz]) X_Acq_Duration = [s] X_Domain = 13C X_Freq = [MHz] X_Offset = 100[ppm] X_Points = X_Prescans = 4 X_Resolution = [Hz] X_Sweep = [kHz] X_Sweep_Clipped = [kHz] Irr_Domain = Proton Irr_Freq = [MHz] Irr_Offset = 5[ppm] Clipped = TRUE Scans = Total_Scans = Relaxation_Delay = 2[s] Recvr_Gain = 60 Temp_Get = 17.8[dC] X_90_Width = 9[us] X_Acq_Time = [s] X_Angle = 30[deg] X_Atn = 6.2[dB] X_Pulse = 3[us] Irr_Atn_Dec = 22.03[dB] Irr_Atn_Noe = 22.03[dB] Irr_Noise = WALTZ Irr_Pwidth = 0.115[ms] Decoupling = TRUE Initial_Wait = 1[s] Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : Carbon Figure S8. 1 H NMR (400 MHz: top) and 13 C NMR (100 MHz: bottom) of A2 in CDCl 3. S22

23 abundance PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 0.2[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm auto_reference( 5[%], TRUE ) X : parts per Million : Proton abundance PROCESSING PARAMETERS ---- dc_balance( 0, FALSE ) sexp( 2.0[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm Filename = gpc02-13C cm-13c-1 Author = delta Experiment = single_pulse_dec.jxp Sample_Id = gpc02-13C Solvent = CHLOROFORM-D Creation_Time = 5-OCT :23:37 Revision_Time = 5-OCT :48:00 Current_Time = 30-MAR :25:12 Data_Format = 1D COMPLEX Dim_Size = Dim_Title = Carbon13 Dim_Units = [ppm] Dimensions = X Site = ECS 400 Spectrometer = DELTA2_NMR Field_Strength = [T] (400[MHz]) X_Acq_Duration = [s] X_Domain = 13C X_Freq = [MHz] X_Offset = 100[ppm] X_Points = X_Prescans = 4 X_Resolution = [Hz] X_Sweep = [kHz] X_Sweep_Clipped = [kHz] Irr_Domain = Proton Irr_Freq = [MHz] Irr_Offset = 5[ppm] Clipped = FALSE Scans = 1000 Total_Scans = 1000 Relaxation_Delay = 2[s] Recvr_Gain = 60 Temp_Get = 25[dC] X_90_Width = 9[us] X_Acq_Time = [s] X_Angle = 30[deg] X_Atn = 6.2[dB] X_Pulse = 3[us] Irr_Atn_Dec = 22.03[dB] Irr_Atn_Noe = 22.03[dB] Irr_Noise = WALTZ Irr_Pwidth = 0.115[ms] Decoupling = TRUE Initial_Wait = 1[s] Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : Carbon Figure S9. 1 H NMR (400 MHz: top) and 13 C NMR (100 MHz: bottom) of A1 in CDCl S23