Supplementary Information for Screening supramolecular interactions between carbon nanodots and porphyrins

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1 Supplementary Information for Screening supramolecular interactions between carbon nanodots and porphyrins Alejandro Cadranel, Volker Strauss, Johannes T. Margraf, Kim A. Winterfeld, Luka Ðorđević, Francesca Arcudi, Helen Hoelzel, Norbert Jux, Maurizio Prato, Dirk M. Guldi Table of Contents Experimental Section S2 Figure S1 S3 Figure S2 S4 Figure S3 S5 Figure S4 S6 Figure S5 S7 Figure S6 S8 Figure S7 S9 Figure S8 S10 Figure S9 S11 Figure S10 S12 Figure S11 S13 Figure S12 S14 Figure S13 S15 Figure S14 S16 Figure S15 S17 Figure S16 S18 Figure S17 S19 Figure S18 S20 Figure S19 S21 Figure S20 S22 Figure S21 S23 Figure S22 S24 Figure S23 S25 Table S1 S26 Table S2 S26 References S27 S1

2 Experimental section Materials Reagents and solvents were purchased (Sigma-Aldrich, Fluorochem, TCI Europe, Acros and Alfa Aesar) and used without further purifications. Deuterated solvents were bought from Cambridge. 5,10,15,20-Tetrakis(4-pyridyl)porphyrin,[1] 5,10,15,20-Tetrakis(N-methyl-4- pyridinio)porphyrin (H2P 4+ ) tetraiodide,[2] Zinc 5,10,15,20-Tetrakis(N-methyl-4- pyridinio)porphyrin (ZnP 4+ ) tetraiodide [3] and Zinc-5,10,15,20-Tetrakis[2',6'-bis(Nmethylene-[4''-t-butylpyridinium])-4'-t-butylphenyl]porphyrin octabromide (ZnP 8+ ) [4] were prepared and characterized according the previously published literature procedures. Physical Measurements Steady state absorption and fluorescence spectroscopy were performed with a Lambda 2 from Perkin Elmer and a Fluoromax-3 from Horiba, respectively. Electrochemical characterization was accomplished with a home- made three-electrode setup connected to a μautolabiii/fra2 potentiostat from Metrohm-Autolab. A 3 mm glassy carbon disk served as a working electrode and a platinum wire was used as a counter electrode. All potentials were measured against a Ag/AgCl reference electrode. Ultrafast transient absorption (TA) experiments were conducted using an amplified Ti/sapphire laser system (Clark MXR CPA2101, FWHM = 150 fs, exc = 450 nm, 200 nj per pulse) with TA pump / probe Helios detection systems from Ultrafast Systems. White light was generated using a sapphire crystal. Optical densities (OD) of the samples were around 0.5 at the excitation wavelengths. A magic angle configuration was employed to avoid rotational dynamics. Globl and Target Analyisis Target analyses were conducted with the GloTarAn software.[5,6] Global analysis by means of a sequential model was employed to derive rates and spectral shapes of the different intermediates following photoexcitation. In cases of porphyrin aggregation or supramolecular interaction between pcnds and the porphyrins, a target analysis was conducted to fit the experimental data to models including branching pathways. S2

3 Figure S1. From top to bottom: Absorption (left) and emission (right) spectra of ZnP 4+, ZnP 8+, ZnP and ZnP 4- (blue, 2x10-6 M) during the course of a titration with pcnd (green to dark red) in methanol at room temperature. ex = 565 nm, 570 nm, 555 nm and 555 nm respectively. Final spectra correspond to pcnd concentrations of 4 mg/l, 10 mg/l, 4 mg/l and 4 mg/l, respectively. S3

4 Figure S2. From top to bottom: Absorption (left) and emission (right) spectra of H2P 4+, H2P 8+, H 2 P and H 2 P 4- (blue, 2x10-6 M) during the course of a titration with pcnd (green to dark red) in methanol at room temperature. ex = 515 nm, 595 nm, 515 nm and 510 nm respectively. S4

5 Figure S3. From top to bottom: Absorption (left) and emission (right, ex = 350 nm) spectra of pcnd (blue, 5 mg/l) during the course of a titration with ZnP 4+, ZnP 8+, ZnP and ZnP 4- (orange to blue, 0 to 2 x 10-5 M) in methanol at room temperature. S5

6 Figure S4. From top to bottom: Absorption (left) and emission (right, ex = 350 nm) spectra of pcnd (blue, 5 mg/l) during the course of a titration with H2P 4+, H2P 8+, H2P and H2P 4- (orange to blue, 0 to 2 x 10-5 M) in methanol at room temperature. S6

7 Figure S5. Relative quenching of the emission of the different porphyrins explored in this work upon the addition of pcnd in methanol at room temperature. S7

8 Figure S6. Square wave voltammograms of ZnP 4+, H2P 4+, ZnP 8+ and H2P 8+ in a 0.1 M solution of TBAPF6 in methanol at room temperature. The peak at V corresponds to the Fc + /Fc internal reference couple. S8

9 Figure S7. Oxidative scans of cyclic voltammograms of H2P 4+ (purple line, 10-4 M) during the course of a titration with pcnds (purple < blue < green < yellow < red lines, g L -1 ) in MeOH. Inset: peak potential versus pcnds concentration. S9

Figure S8. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnds in methanol at room temperature.

10 Figure S8. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnds in methanol at room temperature. Upper right: Time absorption profiles (570 nm as open circles and 740 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnds upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnds upon excitation at 420 nm *pcnd: black, **pcnd: red, ***pcnd: blue. Bottom right: Target model proposed to fit the data. S10

Figure S9. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of H2P 4+ in methanol at room temperature.

11 Figure S9. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of H2P 4+ in methanol at room temperature. Upper right: Time absorption profiles (475 nm as open circles and 720 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for H2P 4+ upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for H2P 4+ upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S11

Figure S10. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of H2P 8+ in methanol at room temperature.

12 Figure S10. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of H2P 8+ in methanol at room temperature. Upper right: Time absorption profiles (460 nm as open circles and 680 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for H2P 8+ upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for H2P 8+ upon excitation at 420 nm S1: black, T: red. Bottom right: Target model proposed to fit the data. S12

13 Figure S11. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of H2P in methanol at room temperature. Upper right: Time absorption profiles (445 nm as open circles and 680 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for H2P upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for H2P upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S13

14 Figure S12. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of H2P 4- in methanol at room temperature. Upper right: Time absorption profiles (445 nm as open circles and 680 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for H2P 4- upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for H2P 4- upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S14

15 Figure S13. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of ZnP 4+ in methanol at room temperature. Upper right: Time absorption profiles (445 nm as open circles and 710 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for ZnP 4+ upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for ZnP 4+ upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S15

16 Figure S14. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of ZnP 8+ in methanol at room temperature. Upper right: Time absorption profiles (465 nm as open circles and 680 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for ZnP 8+ upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for ZnP 8+ upon excitation at 420 nm S1: black, T: red. Bottom right: Target model proposed to fit the data. S16

17 Figure S15. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of ZnP in methanol at room temperature. Upper right: Time absorption profiles (460 nm as open circles and 660 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for ZnP upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for ZnP upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S17

18 Figure S16. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of ZnP 4- in methanol at room temperature. Upper right: Time absorption profiles (460 nm as open circles and 660 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for ZnP 4- upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for ZnP 4- upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S18

Figure S17. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/ H2P 8+ in methanol at room temperature.

19 Figure S17. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/ H2P 8+ in methanol at room temperature. Upper right: Time absorption profiles (460 nm as open circles and 700 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnd/ H2P 8+ upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnd/ H2P 8+ upon excitation at 420 nm S2: black, CT: red, CS: blue, *pcnd: green. Bottom right: Target model proposed to fit the data. S19

20 Figure S18. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/h2p in methanol at room temperature. Upper right: Time absorption profiles (445 nm as open circles and 680 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnd/h2p upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnd/h2p upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S20

21 Figure S19. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/h2p 4- in methanol at room temperature. Upper right: Time absorption profiles (445 nm as open circles and 680 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnd/h2p 4- upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnd/h2p 4- upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S21

Figure S20. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/znp 4+ in methanol at room temperature.

22 Figure S20. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/znp 4+ in methanol at room temperature. Upper right: Time absorption profiles (445 nm as open circles and 710 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnd/znp 4+ upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnd/znp 4+ upon excitation at 420 nm CT: black, CS: red, *pcnd: blue, **pcnd: green. Bottom right: Target model proposed to fit the data. S22

23 Figure S21. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/ ZnP 8+ in methanol at room temperature. Upper right: Time absorption profiles (470 nm as open circles and 710 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnd/ ZnP 8+ upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnd/ ZnP 8+ upon excitation at 420 nm S2: black, CS: red, S1: blue. T: green. Bottom right: Target model proposed to fit the data. S23

24 Figure S22. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/znp in methanol at room temperature. Upper right: Time absorption profiles (460 nm as open circles and 660 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnd/znp upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnd/znp upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S24

25 Figure S23. Upper left: Differential absorption 3D map obtained upon femtosecond pumpprobe experiments (λex = 420 nm) of pcnd/znp 4- in methanol at room temperature. Upper right: Time absorption profiles (460 nm as open circles and 660 nm as open squares) and corresponding fittings from Target Analysis (solid lines) for pcnd/znp 4- upon excitation at 420 nm using the model presented at the bottom right side of this figure. Bottom left: Species associated differential spectra for pcnd/znp 4- upon excitation at 420 nm S(agg): black, S1: red, T: blue. Bottom right: Target model proposed to fit the data. S25

26 Table S1. Time constants extracted from target analysis of the data for the different systems studied in this work, in methanol at room temperature. Sample pcnd ZnP 4+ H 2 P 4+ k 1 / ps -1 ( 1 / ps) ± (6.1) (5.47 ± 0.01) x 10-3 (183) (5.01 ± 0.08) x 10-3 (200) ZnP 8+ - H 2P 8+ - ZnP H 2 P ZnP 4- H 2 P 4- pcnd/znp pcnd/h 2 P pcnd/znp 4- pcnd/h 2 P 4- (8.59 ± 0.06) x 10-3 (116) (1.070 ± 0.008) x 10-2 (94) (3.65 ± 0.03) x 10-3 (274) (2.73 ± 0.03) x 10-3 (366) (10.46 ± 0.01) x 10-3 (96) (9.6 ± 0.1) x 10-3 (105) (1.36 ± 0.02) x 10-3 (736) (3.64 ± 0.06) x 10-3 (275) k 2 / ps -1 ( 2 / ps) (1.39 ± 0.02) x 10-2 (71.9) (6.74 ± 0.01) x 10-4 (1485) (2.8 ± 0.1) x 10-4 (3590) (1.139 ± 0.001) x 10-3 (878) (1.237 ± 0.002) x 10-3 (808) (5.11 ± 0.01) x 10-4 (1958) (1.28 ± 0.02) x 10-4 (7790) (5.23 ± 0.03) x 10-4 (1912) (1.37 ± 0.02) x 10-4 (7290) (4.76 ± 0.02) x 10-4 (2110) (1.40 ± 0.02) x 10-4 (7140) (4.17 ± 0.06) x 10-4 (2398) (1.70 ± 0.02) x 10-4 (5990) k 3 / ps -1 ( 3 / ps) (1.43 ± 0.01) x 10-4 (6990) Table S2. Time constants extracted from target analysis of the data for the different charge separating systems studied in this work, in methanol at room temperature. Sample pcnd/h 2 P 4+ pcnd/znp 4+ pcnd/h 2 P 8+ pcnd/znp 8+ k 1 / ps -1 ( 1 / ps) ± (3.7) ± (2.9) 1.85 ± 0.02 (0.5) 1.50 ± 0.04 (0.7) k 2 / ps -1 ( 2 / ps) (2.90 ± 0.03) x 10-2 (34.5) (2.74 ± 0.03) x 10-2 (36.5) ± (6.4) ± (18.9) k 3 / ps -1 ( 3 / ps) (3.08 ± 0.08) x 10-4 (3200) (1.87 ± 0.02) x 10-4 (5400) (2.68 ± 0.06) x 10-2 (37.3) (3.23 ± 0.05) x 10-3 (310) k 4 / ps -1 ( 4 / ps) S26

27 References [1] Naik, A.; Rubbiani, R.; Gasser, G.; Spingler, B. Visible-Light-Induced Annihilation of Tumor Cells with Platinum-Porphyrin Conjugates. Angew. Chem. Int. Ed. 2014, 53, [2] Ren, Q.-Z.; Yao, Y.; Ding, X.-J.; Hou, Z.-S.; Yan, D.-Y. Phase-Transfer of Porphyrins by Polypeptide-Containing Hyperbranched Polymers and a Novel iron(iii) Porphyrin Biomimetic Catalys. Chem. Commun. 2009, [3] M. Natali, A. Luisa, E. Iengo, F. Scandola, Chem. Commun. 2014, 50, [4] N. Jux, Org. Lett., 2000, Vol. 2, No. 14, [5] van Stokkum, I. H. M.; Larsen, D. S.; van Grondelle, R. Biochim. Biophys. Acta 2004, 1657 (2 3), [6] van Wilderen, L. J. G. W.; Lincoln, C. N.; van Thor, J. J. PLoS One 2011, 6 (3), e S27

Supporting Information

Supporting Information Carbon Nanodots: Supramolecular Electron Donor Acceptor Hybrids Featuring Perylenediimides** Volker Strauss, Johannes T. Margraf, Konstantin Dirian, Zois Syrgiannis, Maurizio Prato,