Supporting Information. Synthesis, Structural and Photophysical Properties of. Pentacene Alkanethiolate Monolayer-Protected Gold

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1 Supporting Information Synthesis, Structural and Photophysical Properties of Pentacene Alkanethiolate Monolayer-Protected Gold Nanoclusters and Nanorods: Supramolecular Intercalation and Photoinduced Electron Transfer with C 60 Daiki Kato, a Hayato Sakai, a Toshiyuki Saegusa, a Nikolai V. Tkachenko, *,b Taku Hasobe *,a a Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama, Kanagawa , Japan b Laboratory of Chemistry and Bioengineering, Tampere University of Technology, Tampere, Finland S1

2 EXPERIMENTAL SECTION General and Materials. All solvents and reagents of the best grade available were purchased from commercial suppliers such as Tokyo Chemical Industry, Kanto Chemical Co.,Inc., Nacalai Tesque, Wako Pure Chemical Industries and Sigma-Aldrich. All commercial reagents were used without further purification. Column flash chromatography was performed on silica gel (Fuji Silysia Chemical LTD., Silica gel 60 N, µm or µm). 1 H NMR and 13 C NMR spectra were recorded on a JEOL ECX-400, AL-400, or ALPHA-400 spectrometer using the solvent peak as the reference standard, with chemical shifts given in parts per million. CDCl 3 was used as a NMR solvent. MALDI-TOF mass spectra were recorded on Bruker Ultra frex. TEM Measurement. Transmission electron micrograph (TEM) measurements were recorded on Tecnai G2 (FEI company) by applying a drop of the sample to a copper grid. TEM images were recorded on a transmission electron microscope at an accelerating voltage of 200 kv for imaging. Spectroscopic Measurements. UV-vis absorption spectra were recorded on Parkin Elmer (Lamda 750) UV-VIS-NIR spectrophotometer. Fluorescence spectra were recorded on Parkin Elmer (LS-55) spectrofluorophotometer. Fluorescence lifetimes were also measured on HORIBA Scientific time-correlated single-photon counting system (FluoroCube) with the laser light (DeltaDiode, laser diode head, 404 nm, pulse width: 50 ps and frequency: 1 MHz, respectively) as an excitation source. The practical time resolution is 15 ps by deconvolution of an observed trace with the analytical software (DAS6). Femtosecond Laser Flash Photolysis. The transient absorption spectroscopy measurements were carried out using a femtosecond pump probe system described elsewhere. 1 In brief, a Libra F laser system (Coherent Inc.) was used to create fundamental light pulses at 800 nm at a repetition rate of 1 khz. The pulse energy was 1 mj, and the pulse duration was approximately 100 fs. The fundamental beam was split in two, and the majority of the beam energy (roughly 90%) was directed to a Topas C optical parametric amplifier (Light Conversion Ltd.) to produce excitation pulses at the desired wavelength. The rest of the fundamental beam was delivered to a white continuum generator (sapphire crystal) for sample probing. The probe beam was split in two to record reference and signal responses. The measurement system (ExciPro, CDP S2

3 Inc.) was equipped with a silicon CCD array for measurements in the visible part of the spectrum, and an InGa diode array for the near-infrared (NIR) wavelengths. The measurements were carried out by comparing responses with and without excitation using a chopper synchronized with the fundamental laser pulses. The spectra were typically acquired by recording 5000 shots, i.e. averaging over 5 s. Excitation energies were sufficiently low to avoid multiple exciton generation; this was verified by recording a series of measurements with different excitation energies for the same sample. No excitation energy dependence of the response was observed. Two wavelength ranges were recorded: visible ( nm) and NIR ( nm). A global fit was applied to the transient absorption data to obtain the so-called decay component spectra, that were used to identify the transient states. The method is described elsewhere. 1 Time profile was analyzed by bi-exponential fitting as follows. OD (t,λ) = Y 0 (λ) + A 1 (λ) exp (-t/τ 1 ) + A 2 (λ) exp (-t/τ 2 ) The fit program also evaluated instrument response, convoluted decays with the response function and compensated group velocity dispersion to obtain true component spectra. Typical instrument response was fs. S3

4 Figure S1. 1 H NMR spectrum of TP-C7-SH. Figure S2. 13 C NMR spectrum of TP-C7-SH. S4

5 10 8 Intensity x Mass, m/z 2000 Figure S3. MALDI-TOF MS spectral profile of TP-C7-SH. Figure S4. 1 H NMR spectrum of TP-C11-SH. S5

6 Figure S5. 13 C NMR spectrum of TP-C11-SH. 7 6 Intensity x Mass, m/z 1200 Figure S6. MALDI-TOF MS spectral profile of TP-C11-SH. S6

7 Table S1. Summary of Elemental Analyses of TP-Cn-X-MPC and TP-Cn-MPR. Compound H / % C / % N / % S / % TP-C7-S-MPC Found Calcd TP-C7-L-MPC Found Calcd TP-C11-S-MPC Found Calcd TP-C11-L-MPC Found Calcd TP-C7-MPR Found TP-C11-MPR Found Table S2. The summarized structural data of TP-Cn-X-MPCs. Mean diameters, number of TP units, TP coverage ratios, and chemical formula estimated by TEM images and elemental analysis. 2 Compound Diameter / nm Number of TP Coverage Chemical Formula TP Units / % TP-C7-S-MPC 1.62 ± C 3021 H 3816 O 53 S 53 Au 149 TP-C7-L-MPC 2.20 ± C 4959 H 6264 O 87 S 87 Au 372 TP-C11-S-MPC 1.65 ± C 3111 H 4080 O 51 S 51 Au 158 TP-C11-L-MPC 2.13 ± C 4575 H 6000 O 75 S 75 Au 338 S7

8 Figure S7. TEM image and corresponding size distribution of (A) TP-C11-S-MPC. (B) TP-C11-L-MPC. S8

9 (A) (B) Figure S8. Large area TEM images of (A) TP-C7-S-MPC and (B) C11-MPR (Undecyl-substituted MPR). S9

10 14 Ion Intensity (arb. unlt) m / z x Figure S9. MALDI-TOF mass spectrum of TP-C7-S-MPC. The maximum peak is ~79,100 (C 3021 H 3816 O 53 S 53 Au 149 : Average mass number: ~71,900 as show in Table S2.) S10

11 25 Ion Intensity (arb. unlt) m / z x Figure S10. MALDI-TOF mass spectrum of TP-C7-L-MPC. The maximum peak is ~137,000 (C 3021 H 3816 O 53 S 53 Au 149 : Average mass number: ~143,000 as show in Table S2.) S11

12 Figure S11. (A) Absorption spectra of (a) TP-C11-S-MPC (0.05 mg/ml), (b) TP-C11-L-MPC (0.05 mg/ml) and (c) TP-Ref (10 µm) and (d) excitation spectrum of TP-C11-S-MPC in toluene (observed at 722 nm). (B) Fluorescence spectra of (a) TP-C11-S-MPC, (b) TP-C11-L-MPC and (c) TP-Ref in toluene (λ ex = 600 nm). Figure S12. (A) Absorption spectra of (a) TP-C11-MPR (0.05 mg/ml), (b) C11-GNR (0.05 mg/ml), and (c) TP-Ref (10 µm), (d) excitation spectrum of TP-C11-MPR in toluene (Observed at 722 nm). (B) Fluorescence spectra of (a) TP-C11-GNR and (b) TP-Ref in toluene (λ ex = 600 nm). S12

13 Figure S13. Fluorescence decay profiles of (a) TP-C11-GNR and (b) TP-Ref in toluene. Excitation wavelength was 404 nm and emission wavelength was 722 nm. S13

14 Figure S14. (A) Fluorescence emission spectra of (a) TP-C11-S-MPC, (b) TP-C11-L-MPC and (c) TP-C11-MPR in toluene at various concentrations of C 60. The excitation wavelength is 325 nm. The concentration of TP on nanocluster or nanorod is 0.1~1.0 µm. (B) Dependence of I 0 /(I 0 I obsd ) on the reciprocal concentrations of C 60. S14

15 Figure S15. Optimized structures of TP-Cn-SH calculated at MM2. S15

16 Figure S16. (A) Femtosecond transient absorption spectra of (A) TP-C11-MPR (50 µm) in toluene. (B) Time profile at 714 nm. S16

17 References 1. Pelado, B.; Abou-Chahine, F.; Calbo, J.; Caballero, R.; de la Cruz, P.; Junquera-Hernández, J. M.; Ortí, E.; Tkachenko, N. V.; Langa, F. Chem. Eur. J. 2015, 21, Kato, D.; Sakai, H.; Tkachenko, N. V.; Hasobe, T. Angew. Chem. Int. Ed. 2016, 55, S17