Unexpected Fluorescence Quenching in a Perylenetetracarboxylate Diimide. Trimer

Transcription

1 Supporting information for: Unexpected Fluorescence Quenching in a Perylenetetracarboxylate Diimide Trimer Yanfeng Wang, Hailong Chen, Haixia Wu, Xiyou Li,* Yuxiang Weng,* Department of Chemistry, Shandong University, Jinan, Shandong , China, Institute of Physics, Chinese Academy of Science, Beijing , China xiyouli@sdu.edu.cn; yxweng@aphy.iphy.ac.cn Contents Page S1: Title of the paper, authors along with the contents. Page S2: 1. General methods. Page S3: 2. Synthesis and structure characterizations of 1-3. Page S6: 3. Absorption spectra of trimer 3 at different concentrations, Figure S1 Page S7: 4. Comparison of the 1 H NMR spectra of monomer1, dimer 2 and trimer 3, Figure S2. Page S8: 5. The excitation spectra of trimer 3, Figure S3. Page S9: 6. Transient absorption spectra of trimer 3 in toluene, Figure S4. S1

2 1. General methods 1 H NMR spectra were recorded on a Bruker DPX 300 spectrometer (300 MHz) in CDCl 3. Spectra were referenced internally by using the residual solvent resonance (δ = 7.26 for CDCl 3 ) relative to SiMe 4. MALDI-TOF mass spectra were taken on a Bruker BIFLEX III ultra-high resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer with α-cyano-4-hydroxycinnamic acid as matrix. Elemental analyses were performed by the Institute of Chemistry, Chinese Academy of Sciences. The absorption spectra were taken on a Hitachi 4100 UV-Vis-NIR spectrometer while the fluorescence spectra were recorded on a K2 system (ISS product) with excitation at 400 nm. The femtosecond time-resolved spectrometer employs a regenerative amplifier Ti:sapphire fs laser with 1-kHz repetition (Hurricane, Spectra Physics) as the primary beam source. The output energy of the laser is 750 mj, with a pulse duration of 150 fs at 800 nm. The output beam was split into two; the one with energy of 6 µj/pulse is focused onto a 2.4-mm thick sapphire plate to generate a white light continuum as a probe source. Another beam was frequency-doubled after passing a translation stage as a pump beam. A dual beam configuration (probe and reference) was adopted for the detection. The probe and reference beams were collected by a pair of objective lenses coupled to a two-branched optical fiber. The spectra were recorded by a charge-coupled device spectrometer (Acton). The delay between the pump and the probe beams was realized by a computer-controlled translation stage. The polarization of the 400 nm pump beam was set to the magic angle (54.7 ) with respect to the probe beam. S2

3 2. Synthesis Column chromatography was carried out on silica gel (Merck, Kieselgel 60, mesh) with the indicated eluents. All other reagents and solvents were used as received.1,3-dihexylamino-5-chloro-2,4,6-triazine, 1 1-hexylamino-3,5-dihyrazine-2,4, 6-triazine, 2 1,3,5-trihyrazine-2,4,6-triazine 3 and 1,7-di(t-butyl)phenoxy-perylene- 9,10-(N-hexyl)dicarboxyimide-3,4-dicarboxyanhydride 2 were prepared following the literature methods. Monomer 1: To a degassed solution of 1,7-di(t-butyl)phenoxy-perylene- 9,10-(N-hexyl)dicarboxyimide-3,4-dicarboxyanhydride (60 mg, mmol) in 30 ml pyridine, 1,3-dihexylamino-5-dihyrazine-2,4,6-triazine (24.36 mg, mmol) was added. The resulted reaction mixture was heated to reflux and kept at reflux for overnight. After cooled to room temperature, the solvents were removed from the mixture under reduced pressure. The residue was purified by column chromatography on silica gel with chloroform / methanol (99.8 / 0.2) as eluent. Monomer 1 was collected as red solid (41 mg, yield 46.4 %). Mp: >280 ºC. 1 H NMR (300 MHz, CDCl 3 ) δ: 9.46 (br, 2H), 8.50 (br, 2H), 8.29 (br, 2H), 7.48 (m, 4H), 7.02(m, 4H), 5.10 (s. 3H), 4.15 (t. 2H), 3.28 (t, 2H), 1.71 (m2h), 1.37 (br, 42H), 0.90 (t, 9h). MALDI-TOF MS (m/z): (M + ), HRMS (m/z): , calcd. for C 65 H 74 N 8 O 6 (m/z): Anal. Calcd. for C 65 H 74 N 8 O 6: C, 73.42; H, 7.01; N, Found: C, 73.32; H, 7.12; N, S3

4 Dimer 2. Following the similar procedures of monomer 1, but with 1-hexylamino-3,5-dihyrazine-2,4,6-triazine (9.34 mg, mmol) instead of 1,3-dihexylamino-5-dihyrazine-2,4,6-triazine. The reaction mixture was column chromatographied on silica gel with chloroform / methanol (99.7 / 0.3) as eluent. Dimer 2 was collected as dark red solid (35 mg, yield 51.6 %). Mp: > 280 ºC. 1 H NMR (300 MHz, CDCl 3 ) δ: 9.25 (br, 1H), (br, 4H), 8.25 (br, 1H), (m, 8H), (m, 8H), (m, 8H), 5.66 (br, 1H), 4.12 (br, 4H), 3.37 (m, 2H), (m, 6H), (m, 54H), (m, 9H). MALDI-TOF MS (m/z): (M+H + ), HRMS(m/z): (M+H + ), calcd. for C 109 H 106 N 10 O 12 (m/z): Anal. Calcd. for C 109 H 106 N 10 O 12: C, 74.89; H, 6.11; N, Found: C, 75.21; H, 6.21; N, Trimer 3. Prepared with the similar procedure of monomer 1 but with 1,3,5-trihyrazine-2,4,6-triazine (5.1 mg, mmol) instead of 1,3-dihexylamino -5-dihyrazine-2,4,6-triazine. The product was separated from the reaction mixture by column chromatography on silica gel with chloroform / methanol (99.5 / 0.5) as eluent. Trimer 3 was collected as dark red solid (27 mg, yield 28.5 %). Mp: > 280 ºC. 1 H NMR (300 MHz, CDCl 3 ) δ: 9.45 (br, 2H), 9.26 (br, 1H), 9.08 (br, 4H), (br, 2H), (m, 3H), (m, 9H), (m, 12H), (m, 12H), (m, 6H), 1.71 (br, 6H), (m, 72H), 0.88 (m, 9H). MALDI-TOF MS (m/z): (M+H + ), HRMS (m/z): (M+H + ), calcd. for C 153 H 138 N 12 O 18 (m/z): Anal. Calcd. for C 153 H 138 N 12 O 18: C, 75.54; H, 5.72; N, Found: S4

5 C, 75.33; H, 5.56; N, Reference: (1) Bielejewska, A. G.; Marjo, C. E.; Prins, L. J.; Timmerman, P.; Jong, F.; Reinhoudt, D. N. J. Am. Chem. Soc. 2001, 123, (2) Wang, Y.; Chen, Y.; Li, R.; Wang, S.; Su, W; Ma, P.; Wasielewski, M. R.; Li, X.; Jiang, J. Langmuir 2007, 23, (3) Würthner, F.; Thalacker, C.; Sautter, A. Adv. Mater. 1999, 11, S5

6 3. Absorption spectra of compound 3 at different concentrations Figure S1. Absorption spectra of trimer 3 at different concentration. (black, 1 X 10-6 mol L -1 ; blue, 1 X 10-5 mol L -1 ; red, 1 X 10-4 mol L -1 ). S6

7 4. Comparison of the 1 H NMR spectra of monomer1, dimer 2 and trimer 3. Figure S2. The 1 H NMR spectra of monomer 1, dimer 2 and trimer 3 in CDCl 3. The spectra of trimer 3 show clearly the signal groups of both dimer and monomer. S7

8 5. The excitation spectra of trimer 3. Figure S3. The normalized excitation spectra of trimer 3 (black) compared with the absorption spectra of dimer 2 (red). The difference at about 542 nm suggests the presence of the contribution from monomer s absorption to the dimer s emission. S8

9 6. Transient absorption spectra of trimer 3 in toluene Figure S4. Transient absorption spectra of trimer 3 in toluene after a 150 fs laser pulse excitation at 400 nm. S9