Supporting Information

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1 Supporting Information Photoinduced Processes of Subphthalocyanine Diazobenzene Fullerene Triad as an Efficient Excited Energy Transfer System Jong-Hyung Kim, 1 Mohamed E. El-Khouly,* 2,3 Yasuyuki Araki, 2 samu Ito, 2 and Kwang-Yol Kay* 1 1 Department of Molecular Science and Technology, Ajou University, Suwon , Korea 2 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Sendai Department of Chemistry, Faculty of Education, Kafr El-Sheikh University, Egypt (Received February 20, 2008; CL ; kykay@ajou.ac.kr) Copyright The Chemical Society of Japan

2 Supporting Information Photoinduced Processes of Suphthalocyanine Diazobenzene-Fullerene Triad as an Efficient Excited Energy Transfer System Jong-Hyung Kim, 1 Mohamed E. El-Khouly,* 2,3 Yasuyaki Araki, 2 samu Ito 2 and Kwang-Yol Kay* 1 1 Department of Molecular Science and Technology, Ajou University, Suwon , South Korea. kykay@ajou.ac.kr 2 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Sendai, , Japan. araki@tagen.tohoku.ac.jp 3 Department of Chemistry, Faculty of Education, Kafr El-Sheikh University, Egypt, E- mail: mohamedelkhouly@yahoo.com Experimental Section Materials and instruments; Reagents and solvents were purchased as reagent grade and used without further purification. All reactions were performed using dry glassware under nitrogen atmosphere. Analytical TLC was carried out on Merck 60 F254 silica gel plate and column chromatography was performed on Merck 60 silica gel ( mesh). Melting points were determined on an Electrothemal IA 9000 series melting point apparatus and are uncorrected. MR spectra were recorded on a Varian Mercury-400 (400 MHz) spectrometer with TMS peak as reference. UV/Vis spectra were recorded on a Jasco V-550 spectrometer. MALDI-TF MS spectra were recorded with an Applied Biosystems Voyager-DE-STR. Elemental analyses were performed with a Perkin-Elmer 2400 analyzer. 1

3 Synthesis 2 H a) H 2 H b) H H c) 2 3 H H d) 4 B 6 H e) B C 8 H 17 C C BCl 3 B 5 Cl SubPc diazobenzene C 60 (1) Scheme S1. Synthesis of compound 1. a) ash, H 2, 95 o C, 3h, 77.5%. b) sodium nitrate, conc. HCl, H 2, 5 o C, 1h and then phenol, H 2, K 2 C 3, rt, 3h, 96.1%. c) PCC, THF, reflux, 63.3%. d) compound 5, toluene, reflux, 36h, 63.9%. e) C 60, -octylglycine, chlorobenzene, reflux, 4h, 34.0%. 4-Aminobenzylalcohol (2). To a solution of 70% ash (16.0g, 200mmol) in water (130ml) was added 4-nitrobenzyl alcohol (15.31g, 100mmol) and was stirred at 95 o C, for 3h. The reaction mixture was cooled to room temperature and then extracted with ethyl acetate (3 x 100ml). The extract was dried over MgS 4, and evaporated to give compound 2 (9.54g, 77.5%) in a brown solid. M.p o C ; 1 H-MR (400MHz, CDCl 3 ) : δ = 7.10 (d, J = 8.2 Hz, 2H), 6.62 (d, J = 8.2 Hz, 2H), 4.75 (s, 2H). 4,4 -Hydroxyphenylazobenzylalcohol (3). The suspension of compound 2 (9.37g, 76.1ml) in water (135ml) was cooled to 5 o C and conc. HCl (15.8ml, 190mmol) was added to the mixture. To the reaction mixture was added the cooled (5 o C) solution of sodium nitrate (5.03g, 79.8mmol) in water (35ml) and stirred at 5 o C. After 1h, the 2

4 solution of phenol (7.52g, 79.9mmol), K 2 C 3 (15.0g, 108.5mmol) in water (120ml) dropwised to the reaction mixture for 10min and stirred at room temperature for 3h. After the reaction was completed, dilute acetic acid was added to the mixture and adjusted to ph 4. The product was filtered, and washed with water, methanol to give compound 3 (16.70g, 96.1%) in a yellow solid. M.p o C ; 1 H-MR (400MHz, aceton-d 6 ) : δ = 7.86 (m, 4H), 7.54 (d, J = 8.4 Hz, 2H), 7.02(d, J = 8.4 Hz, 2H), 4.73(s, 2H). ; Anal. Calcd for C 13 H : C, 68.41% ; H, 5.30% ;, 12.27%. Found : C, 68.40% ; H, 5.41% ;, 12.24%. 4,4 -Hydroxyphenylazobenzcarboxaldehyde (4). To a solution of compound 3 (0.50g, 2.19mmol) in THF (10ml) was added pyridinium chlorochromate (0.71g, 3.29mmol) and refluxed for 2h. After cooling, the solution was filtered and evaporated. The product was chromatographed on silica gel with dichloromethane/ methanol (20:1) to give compound 4 (0.31g, 63.3%) in a yellow solid. M.p o C ; 1 H-MR (400MHz, aceton-d 6 ) : δ = (s, 1H), 8.08 (d, J = 8.4 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H), 7.90 (d, J = 8.4 Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H).; Anal. Calcd for C 13 H : C, 69.02% ; H, 4.46% ;, 12.38%. Found : C, 69.01% ; H, 4.53% ;, 12.35%.. SubPc diazobenzene aldehyde (6). To a solution of compound 4 (53mg, 3mmol) in toluene (10ml) was added compound 5 [1] (50mg, 0.12mmol) and refluxed for 36h. The reaction mixture was cooled to room temperature and evaporated. The product was chromatographed on silica gel with dichloromethane/ methanol (20:1) to give compound 6 (46mg, 63.9%) in a purple solid. M.p o C ; 1 H-MR (400MHz, CDCl 3 ) ; δ = 11 (s, 1H), 8.84 (dd, J = 3.2 Hz, J = 3.2 Hz, 6H), 7.90 (m, 8H), 7.81 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 8.8 Hz, 2H), 5.48 (d, J = 8.8 Hz, 2H).; Anal. Calcd for C 37 H 21 8 B 2 : C, 71.63% ; H, 3.41% ;, 18.06%. Found : C, 71.60% ; H, 3.44% ;, 18.05%. SubPc diazobenzene C 60 (1). Compound 6 (40mg, 64mmol) and -octylglycine [2] (14mg, 76mmol) were added to a solution of fullerene (47mg, 64mmol) in chlorobenzene (7ml). The reaction mixture was refluxed for 4h, and then filtered off. The filtrate was evaporated and chromatographed on silica gel with toluene/acetone (20:1) to 3

5 give compound 1 (32mg, 34.0%) in a black solid. M.p. > 410 o C (dec.) ; 1 H-MR (400MHz, CS 2 : CDCl 3 = 10 : 1) ; δ = 8.73 (m, 6H), 7.82 (m, 8H), 7.72 (br, 2H), 7.27 (d, J = 8.8 Hz, 2H), 5.33 (d, J = 8.8 Hz, 2H), 4.96 (d, J = 9.6 Hz, 1H), 4.94 (s, 1H), 3.98 (d, J = 9.6 Hz, 1H), 3.18 (t, 2H), (br, 12H), 0.90 (m, 3H). ; 13 C-MR (400MHz, CS 2 : CDCl 3 = 10 : 1) ; δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 136, , , , , 82.67, 76.86, 69.10, 67.33, 53.95, 32.93, 30.70, 31, 29.40, 28.51, 23.89, ; UV/Vis (toluene) : λ max = 313, 433, 523, 545, 563 nm ; MS (MALDI-TF) ; m/z for C 106 H 40 9 B Calcd Found ; Anal. Calcd : C, 86.82% ; H, 2.75% ;, 8.60%. Found : C, 86.81% ; H, 2.77% ;, 8.58%. References 1. C. G. Claessens, D. González-Rodíguez, B. del Rey, T. Torres, Eur. J. rg. Chem. 2003, C. M. Deber, P. D. Adawadkar, P. D. Biopolymers. 1979, 18,

6 Photo-physical measurements Steady-state absorption and fluorescence spectra were measured on a JASC V-550 spectrometer (UV-Vis-IR) and Shimadzu spectrofluorophotometer equipped with a photomultiplier tube having high sensitivity in the longer wavelength region, respectively. The picosecond time-resolved fluorescence spectra were measured by a single-photon counting method using a second harmonic generation (SHG, 400 nm) of a Ti:sapphire laser (Spectra-Physica, Tsunami 3950-L2S, 1.5 ps fwhm) and a streak-scope (Hamamatsu Photonics) equipped with a polychromator as an excitation source and a detector, respectively. Lifetimes were evaluated with software attached to the equipment. The nanosecond transient absorption measurements in the near-ir region were measured by laser-flash photolysis; 355 nm light from a d:yag laser (Spectra-Physics and Quanta-Ray GCR-130, 6 ns fwhm) was used as an excitation source. The monitoring lights from a pulsed Xe-lamp were detected via Ge-avalanche photodiode module. The samples were held in a quartz cell (1 1 cm) and were deaerated by bubbling argon gas through the solution for 20 minutes. Time-resolved Fluorescence spectra Figure S1.Time-resolved spectra of SubPc Ph=Ph C 60 in toluene; λ ex = 532 nm laser light with 10 ps time-resolution.. 5

7 anosecond transient spectra ΔAbsorbance µs 1.0 µs ΔAbs Time / µs Wavelength / nm 700 nm ΔAbsorbance ΔAbs 700 nm Time / µs Wavelength / nm 1200 Figure S2. Transient of SubPc Ph=Ph C 60 in toluene (upper) and B (lower); λ ex = 532 nm laser light. 1 SubPc* Ph=Ph C nm EnT SubPc Ph=Ph 1 C 60 * ISC SubPc Ph=Ph 3 C 60 * k T SubPc Ph=Ph C 60 Figure S3. Energy diagrams of SubPc Ph=Ph C 60 6