Supporting Information

Transcription

1 Supporting Information Carbon Nanodots: Supramolecular Electron Donor Acceptor Hybrids Featuring Perylenediimides** Volker Strauss, Johannes T. Margraf, Konstantin Dirian, Zois Syrgiannis, Maurizio Prato, Cordula Wessendorf, Andreas Hirsch, Timothy Clark, and Dirk M. Guldi* anie_ _sm_miscellaneous_information.pdf

2 Supporting Information Experimental Details... S2 Steady State Characterization... S3 Electrochemical Characterization... S5 Steady State Absorption and Emission Titrations... S7 Calculations... S10 TCSPC... S11 Femtosecond Transient Absorption... S12 S1

3 Experimental Details The synthetic procedure of pcnds followed our mild microwave synthesis protocol. Urea and citric acid were mixed in a molar ratio of 3:1 and reacted in a microwave reactor at 150 C and 15 bar for 5 min. The product was precipitated in acetone to remove excess of the precursors. Then the product was washed in MeOH several times. In the last step, the solvent was evaporated at 70 C. The remaining solid was used for further analysis. PDI 1 was synthesized in the Group of Maurizio Prato and published elsewhere. 1,2 PDI 2 was synthesized in the Group of Andreas Hirsch and published elsewhere. 3 Fluorescence quantum yields were determined in H 2 O by the gradient method against Sulforhodamin B as a reference. Steady-state Absorption measurements were carried out with a Lambda 2 UV/Vis/NIR-spectrometer (Perkin Elmer) or a Cary 5000 UV/Vis/NIR-spectrometer (Varian). Steady-state fluorescence emission measurements were performed with a FluoroMax -3 (Horiba). Time-correlated single-photon counting was perfomed with a FluoroLog -3 spectro-fluorometer (Horiba). All spectra were corrected for the instrument response. Femtosecond transient-absorption studies were carried out using a transient absorption pump/probe system (Clark-MXR Inc.) connected to a CPA-2101 laser M phosphate buffer solutions in D 2 O were used for all spectroscopic measurements unless otherwise noted. Voltammetric measurements were performed with a three-electrode setup using a 3 mm glassy carbon disk as working electrode, a platinum wire as counter-electrode, and Ag/AgCl reference electrode. The solutions were thoroughly deoxygenated prior to the measurements. [1] B. Wang, C. Yu, Angew. Chem. Int. Ed. Engl. 2010, 49, [2] Y. Huang, Y. Yan, B. M. Smarsly, Z. Wei, C. F. J. Faul, J. Mater. Chem. 2009, 19, [3] C. D. Schmidt, C. Böttcher, A. Hirsch, Eur. J. Org. Chem. 2007, S2

4 Steady State Characterization Figure S1. Normalized absorption (solid line, c = M) and fluorescence (dashed line, λ ex = 500 nm, c = M) spectra of 1 in D 2 O. Figure S2. Normalized steady state absorption (solid line, c = M) and fluorescence (dashed line, λ ex = 500 nm, c = M) spectra of 2 in D 2 O. S3

5 Figure S3. Normalized absorption (solid line, c = M) and fluorescence (λ ex = 350nm, dashed line, and 500 nm, dotted line) spectra of pcnd in D 2 O. S4

6 Electrochemical Characterization Figure S4. Cyclic voltammograms (above) and differential pulse voltammograms (below) of 1 (blue line) and pcnd (red line) in D 2 O with NaCl as supporting electrolyte (negative scan direction: dark blue line and dark red line, positive scan direction: light blue line and light red line) Figure S5. Left: Cyclic voltammograms of 2 in a phosphate buffer solution in H 2 O (left) and in MeOH (right). S5

7 Figure S6. Differential pulse voltammograms of pcnd in MeOH (negative scan direction: red line, positive scan direction: black line). S6

8 Steady State Absorption and Emission Titrations Figure S7. Absorption spectra of 2 (black spectrum, 10-5 M) during the course of a titration with pcnd (dark red>light red, g L 1 ) in phosphate-buffered D 2 O (ph=7.2) at room temperature. Figure S8. Fluorescence spectra of 2 (black spectrum, 10-5 M) during the course of a titration with pcnd (dark red>light red, g L 1 ) in phosphate-buffered D 2 O (ph=7.2) at room temperature. Figure S9. Absorption spectra of pcnd (black, 0.2 g L 1 ) (black spectrum) during the course of a titration with 1 (dark red>light red, M) in phosphate-buffered D 2 O (ph=7.2) at room temperature. S7

9 Figure S10: Absorption spectra of pcnd (black, 0.2 g L 1 ) (black spectrum) during the course of a titration with 2 (dark red>light red, M) in phosphate-buffered D 2 O (ph=7.2) at room temperature. Figure S11. Left: fluorescence spectra of pcnd (black spectrum, 0.2 g L 1 ) during the course of a titration with 1 (dark red>light red, M) in phosphate-buffered D 2 O (ph=7.2) at room temperature. Right: relationship of I/I 0 to the concentration of 1 used to determine the association constant. Figure S12. Fluorescence spectra of pcnd (black spectrum, 0.2 g L 1 ) during the course of a titration with 2 (dark red>light red, M) in phosphate-buffered D 2 O (ph=7.2) at room temperature. Below; relationship of I/I 0 to the concentration of 2 used to determine the association constant S8

10 Figure S13. Left Fluorescence spectra of pcnd/1 (black) during the course of a titration with variable amounts of KCl in D 2 O at room temperature (dark red>light red). Right Integrated emission intensity versus KCl concentration. Figure S14. Absorption spectra of 1 (black) and pcnd/1 during the course of a titration with variable amounts of KCl in D 2 O at room temperature (dark red>light red). Figure S15. Left: reductive scans of cyclic voltammograms of 1 (black spectrum, M (0.5 g L 1 )) during the course of a titration with pcnd (purple>blue>green>yellow>red spectra, 0-15 g/l) in H 2 O with NaCl as supporting electrolyte. Right; peak potential versus the concentration of pcnd that was used to determine the association constant. S9

11 Calculations Figure S16. Simulated UV-vis absorption spectrum spectrum of pcnd/1 using PM6. S10

12 TCSPC Figure S17. Fluorescence-time profiles of pcnd (blue), 1 (dark red) and 1/pCND (red) in D 2 O at room temperature obtained by TCSPC upon excitation at 500 nm. Figure S18: Fluorescence-time profiles of pcnd (blue), 2 (dark red) and 2/pCND (red) in D 2 O at room temperature obtained by TCSPC upon excitation at 500 nm. Table S1: Lifetimes of pcnds and pcnd/1 obtained by TCSPC at 445 nm upon excitation at 403 nm. τ 1 [ns] τ 2 [ns] τ 3 [ns] pcnd 2.1 (32%) 5.8 (30%) 11.1 (38%) pcnd/1 0.6 (22%) 2.5 (37%) 7.3 (42%) Table S2: Lifetimes of 1 and 1/pCND obtained by TCSPC at 550 nm upon excitation at 403 nm. τ 1 [ns] τ 2 [ns] τ 3 [ns] (2%) 4.7 (98%) 1/pCND 0.2 (13%) 4.7 (87%) S11

13 Femtosecond Transient Absorption Figure S19. Left: differential absorption spectra obtained upon femtosecond pump probe experiments (500 nm) of 1 ( M) in phosphate-buffered D 2 O (ph=7.2) with several time delays in ps between 0 and 5000 ps at room temperature. Right: time absorption profiles of the spectra shown in the above at 500 nm (blue), 591 nm (magenta), 850 nm (black), and 1000 nm (red) monitoring the singlet excited state decay. 2 (λ ex = 500 nm) Figure S20. Left: Differential absorption spectra obtained upon femtosecond pump probe experiments (500 nm) of 2 in D 2 O with several time delays between 5 and 5000 ps at room temperature. Right: Time-absorption profiles of the spectra shown in the upper part at 500 (black), 591 (red), 850 (blue), and 1000 nm (magenta) monitoring the excited state decay. S12

14 2/pCND (λ ex = 500 nm) Figure S21. Left: Differential absorption spectra obtained upon femtosecond pump probe experiments (500 nm) of 2/CND in D 2 O with several time delays between 0 and 5000 ps at room temperature. Right: Time-absorption profiles of the spectra shown in the upper part at 500 (black), 591 (red), 850 (blue), and 1000 nm (magenta) monitoring the excited state decay. S13

15 1 (λ ex = 387 nm) Figure S22. Left: Differential absorption spectra obtained upon femtosecond pump probe experiments (387 nm) of 1 in D 2 O with several time delays between 5 and 5000 ps at room temperature. Right: Time absorption profiles of the spectra shown in the upper part at 500 (black), 591 (red), 850 (blue), and 1000 nm (magenta) monitoring the excited state decay. 1/pCND (λ ex = 387 nm) Figure S23. Left: Differential absorption spectra obtained upon femtosecond pump probe experiments (387 nm) of 1/CND in D 2 O with several time delays between 0 and 5000 ps at room temperature. Right: Time absorption profiles of the spectra shown in the upper part at 500 (black), 591 (red), 850 (blue), and 1000 nm (magenta) monitoring the excited state decay. S14

16 2 (λ ex = 387 nm) Figure S24. Left: Differential absorption spectra obtained upon femtosecond pump probe experiments (387 nm) of 2 in D 2 O with several time delays between 0 and 5000 ps at room temperature. Right: Time absorption profiles of the spectra shown in the upper part at 500 (black), 591 (red), 850 (blue), and 1000 nm (magenta) monitoring the excited state decay. 2/pCND (λ ex = 387 nm) Figure S25. Left: Differential absorption spectra obtained upon femtosecond pump probe experiments (387 nm) of 2/CND in D 2 O with several time delays between 0 and 5000 ps at room temperature. Right: Time absorption profiles of the spectra shown in the upper part at 500 (black), 591 (red), 850 (blue), and 1000 nm (magenta) monitoring the excited state decay. S15