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Catalytically Efficient Palladium anoparticles Stabilized by Click rrocenyl Dendrimers Cátia rnelas, Lionel Salmon, Jaime Ruiz Aranzaes, Didier Astruc Supplementary Information Cyclic Voltammetry (CV), UV-Vis spectroscopy, 1 H MR and Transmition Electron Microscopy (TEM) data. Cyclic voltammetry measurements: All electrochemical measurements were recorded under nitrogen atmosphere. Conditions: solvent: Chloroform/Methanol (2:1); temperature: 20ºC; Supporting electrolyte: [nbu 4 ][PF 6 ] 0.1M; working and counter electrodes: Pt; reference electrode: Ag; internal reference: Cp 2 * (Cp*= η 5 -C 5 Me 5 ); scan rate: 0.200 Vs -1. Gas Chromatography: GC data were recorded on a Hewlett Packard 5890 Series II gas chromatograph, equipped with a Stabilwax (Crossband Carbowax -PEG) column and a flame ionization detector. For all substrates Helium was used as the carrier gas. The injector and detector temperature were 240 ºC. Transmission Electron Microscopy (TEM): Samples were prepared placing a drop of a 4.41x10-4 M solution (CHCl 3 /MeH 2:1) of palladium nanoparticles (concentration in mol Pd) on a holey-carbon-coated Cu TEM grid. The size of the nanoparticles was measured using the software sigmascanpro (for each sample, about 100 nanoparticles were measured). (The theoretical diameter of the palladium nanoparticles were calculated using the equation n = 4π r 3 / 3V g, where n is the number of Pd atoms, r is the radius of the Pd nanoparticle and V g is the volume of one Pd atom (15 Å 3 )) 12 General procedure for the preparation of PdPs (the procedure is described using preparation of DS-G 0 as an example): Method 1: 2 ml of a 3x10-4 M solution of dendrimer G 0 (2.0 mg, 5.87x10-4 mmol) in chloroform was placed in a schlenk flask under nitrogen. 1.2 ml of a 4.5x10-3 M

chloroform solution of Pd(Ac) 2 (1.2 mg, 5.28x10-3 mmol, 1 equiv. per triazole) was added. Chloroform (0.8 ml) and methanol (2 ml) were added in order to obtain a solution 8.82x10-4 M (in Pd), 2:1 (CHCl 3 /MeH). The solution was stirred for 5 minutes and abh 4 (2 mg, 5.87x10-2 mmol, 10 equiv. per Pd) was added and the yellow solution turned to golden brown indicating the nanoparticle formation. Method 2: 2 ml of a 3x10-4 M solution of dendrimer G 0 (2.0 mg, 5.87x10-4 mmol) in chloroform was placed in a schlenk flask under nitrogen. 1.2 ml of a 4.5x10-3 M chloroform solution of Pd(Ac) 2 (1.2 mg, 5.28x10-3 mmol, 1 equiv. per triazole) was added. Chloroform (0.8 ml) and methanol (2 ml) were added in order to obtain a solution 8.82x10-4 M (in Pd), 2:1 (CHCl 3 /MeH). The solution was stirred for 16 h and the yellow solution turned to golden brown indicating the nanoparticle formation. Hydrogenation reactions: In a schlenck flask, the nanoparticles were freshly prepared in order to obtain a solution 8.82x10-4 M (in Pd), in CHCl 3 /MeH (2:1) and 1000 equiv. of the substrate was added. The schlenck was filled with H 2 (1 atm) and the solution was allowed to stir at 25ºC. Re-using the catalyst: substrate was added to the reaction solution until the catalyst was no longer active. Calculation of the Turn ver Frequency (TF): several samples of the reaction solution were extracted at different times of reaction, and analyzed. Calculation of the Turn ver umber (T): The sum of substrate that reacted in all the catalytic cycles effectuated, after analyzing the final reaction solution.

Cyclic Voltammetry Data Titrations of Pd(Ac) 2 followed by cyclic voltammetry (CV): General method: The supporting electrolyte was introduced into the electrochemical cell containing the working electrode, the reference electrode and the counter electrode. After dissolving in chloroform/methanol (2:1), a blank voltammogram was recorded to check the working electrode. A chloroform/methanol (2:1) solution of dendrimer and internal reference were added to the cell, and the CV was recorded. Then, small amounts of a chloroform solution of Pd(Ac) 2 was added with a microsyringe. After each addition, the solution was degassed, and the CV was recorded. The appearance and progressive increase of a new wave was observed, while the initial wave decreased and finally disappeared. When the initial wave had completely disappeared, addition of the Pd(Ac) 2 solution was continued until reaching twice the volume already introduced. Conditions: solvent: chloroform/methanol (2:1); temperature: 20ºC; Supporting electrolyte: [nbu 4 ][PF 6 ] 0.1M; working and counter electrodes: Pt; quasi-reference electrode: Ag; internal reference: Cp 2 *; scan rate: 0.200 Vs -1. Table 1. Cyclic voltammetry results of the recognition of the Pd(Ac) 2 by the poly- 1,2,3-triazolylferrocenyl dendrimers. Dendrimer umber of triazole units (interior + exterior) E 1/2 [a] (E pa -E pc ) (V) Recognition of Pd(Ac) 2 E 1/2 (E pa -E pc ) (V) E 1/2 [b] (V) K (0) /K (+) [c] 1- G 0 9 0.540 0.640-0.100 53 (0.050) (0.030) 36 0.540 0.625 2- G 1-0.085 29 (0.030) (0.020) 117 0.540 0.595 3- G 2-0.055 9 (0.030) (0.020) [a] E 1/2 = (E pa +E pc )/2 vs. Cp 2 * (in V). Electrolyte: [nbu 4 ][PF 6 ] 0.1M; solvent: chloroform/methanol (2:1); working and counter electrodes: Pt; quasi-reference electrode: Ag; internal reference: Cp 2 *; scan rate: 0.200 Vs -1 ; 20 C. [b] Difference between values of E 1/2 before (3 rd column) and after (4 th column) titration. [c] Ratios of apparent association constants; error 10%; E 1/2 = 0.058 log(k (0) /K (+) )at 20 C. [E.S.I.1] [E.S.I.1] Miller, S. R.; Gustowski, D. A.; Chen, Z.-H.; Gokel, G. W.; Echegoyen, L.; Kaifer, A. E. Anal. Chem. 1988, 60, 2021-2024.

Titration of Pd(Ac) 2 with poly-1,2,3-triazolylferrocenyl dendrimer G 0 Figure 1. a) CV of G 0 (c = 1.47x10-4 M) before addition Pd(Ac) 2 ; b) CV of G 0 during titration of Pd(Ac) 2 (0.5 equiv. per triazole); c) CV of G 0 at the end of titration of Pd(Ac) 2 (1 equiv. per triazole). I (µa) 11 10 9 8 7 6 5 4 3 2 1 0 0 5 10 15 20 Equiv. of Pd(Ac) 2 per Dendrimer G 0 Figure 2. Titration of Pd(Ac) 2 with G 0 (c = 1.47x10-4 M). Decrease of the intensity of the initial CV wave ( ) and increase of the new CV wave ( ) vs the number of equiv. of Pd(Ac) 2 added per Dendrimer G 0.

Titration of Pd(Ac) 2 with poly-1,2,3-triazolylferrocenyl dendrimer G 1 Figure 3. a) CV of G 1 (c = 4.89x10-4 M) before addition Pd(Ac) 2 ; b) CV of G 1 during titration of Pd(Ac) 2 (0.6 equiv. per triazole); c) CV of G 1 at the end of titration of Pd(Ac) 2 (1 equiv. per triazole). 5 4 I (µa) 3 2 1 0 0 20 40 60 80 Equiv. of Pd(Ac) 2 per Dendrimer G 1 Figure 4. Titration of Pd(Ac) 2 with G 1 (c = 4.89x10-4 M). Decrease of the intensity of the initial CV wave ( ) and increase of the new CV wave ( ) vs the number of equiv. of Pd(Ac) 2 added per Dendrimer G 1.

Titration of Pd(Ac) 2 with poly-1,2,3-triazolylferrocenyl dendrimer G 2 Figure 5. a) CV of G 2 (c = 1.63x10-5 M) before addition Pd(Ac) 2 ; b) CV of G 2 during titration of Pd(Ac) 2 (0.65 equiv. per triazole); c) CV of G 2 at the end of titration of Pd(Ac) 2 (1 equiv. per triazole). 5 4 I (µa) 3 2 1 0 0 50 100 150 200 250 Equiv. of Pd(Ac) 2 per Dendrimer G 2 Figure 6. Titration of Pd(Ac) 2 with G 2 (c =1.63x10-5 M). Decrease of the intensity of the initial CV wave ( ) and increase of the new CV wave ( ) vs the number of equiv. of Pd(Ac) 2 added per Dendrimer G 2.

UV/Vis. spectra 0.7 0.6 b) a) 0.5 A 0.4 0.3 0.2 ew band 0.1 0.0 300 400 500 600 700 Wavelength (nm) Figure 7. a) UV/Vis spectrum of a freshly prepared 7.43x10-5 M solution of Pd(Ac) 2 in CHCl 3 /MeH (2:1); b) Uv/visible spectra of a solution of G 0 (8.26x10-6 M) and 9 eq. of Pd(Ac) 2 (7.43x10-5 M) in CHCl 3 /MeH (2:1) after 30 min (using a 7.43x10-5 M solution of Pd(Ac) 2 in CHCl 3 /MeH (2:1) as blank), after 16h a similar spectra was obtained. 2 a) b) c) A 1 Initial band Completly disparition of the initial band upon addition of G 0 0 300 400 500 600 700 wavelength (nm) Figure 8. a) UV/Vis. spectrum of a freshly prepared 2.97x10-3 M solution of Pd(Ac) 2 in CHCl 3 /MeH (2:1); b) UV/Vis. spectrum of a solution of G 0 (9.78x10-5 M) and 9 eq. of Pd(Ac) 2 (8.80x10-4 M) in CHCl 3 /MeH (2:1) after 30 min (using a 9.78x10-5 M solution of dendrimer in CHCl 3 /MeH (2:1) as blank); c) UV/Vis. spectrum of the PdP obtained by reduction with abh 4 (similar spectra was obtained using MeH as reductant).

Transmission Electron Microscopy (TEM) data a) 50 nm Frequency % 40 35 1.2 ± 0.2 nm b) 30 25 20 15 10 5 0 0.8-1.0 1.0-1.2 1.2-1.4 1.4-1.6 1.6-1.8 Diameter (nm) Figure 9. DE-G 0 /method 1: a) TEM image and b) size distribution. a) Frequency % 40 35 2.8 ± 0.3 nm 30 25 20 15 10 5 0 2.0-2.3 2.3-2.6 2.6-2.9 2.9-3.2 3.2-3.5 Diameter (nm) Figure 10. DE-G 0 /method 2: a) TEM image and b) size distribution. b) Figure 11. DE-G 1 /method 1: a) TEM image and b) size distribution.

Figure 12. DE-G 1 /method 2: a) TEM image and b) size distribution. Figure 13. DE-G 2 /method 1: a) TEM image and b) size distribution. Figure 14. DE-G 2 /method 2: a) TEM image and b) size distribution.

Figure 15. DE-G 2-36/method 1: a) TEM image and b) size distribution. Figure 16. DE-G 2-36/method 2: a) TEM image and b) size distribution. Figure 17. DE-PAMAM/method 1: a) TEM image and b) size distribution.

MR Spectra of Pd(Ac) 2 complexation Figure 18. 1 H MR spectrum of the blank CDCl 3 /MeD (2:1). Figure 19. 1 H MR spectrum of G 0 in CDCl 3 /MeD (2:1).

Figure 20. 1 H MR spectrum of Pd(Ac) 2 in CDCl 3. Figure 21. 1 H MR spectrum of Pd(Ac) 2 in CDCl 3 /MeD (2:1) after 5 min.

Figure 22. 1 H MR spectrum of G 0 and 9 eq. of Pd(Ac) 2 in CDCl 3 ; no interaction is observed. Figure 23. 1 H MR spectrum of G 0 and 9 eq. of Pd(Ac) 2 in CDCl 3 /MeD (2:1) after 1 min.

Figure 24. 1 H MR spectrum of G 0 and 9 eq. of Pd(Ac) 2 in CDCl 3 /MeD (2:1) after 10 min. CH 3 H 3 C CH 3 CH 3 H H H H Figure 25. Chemical structure of Ergosterol.

Table 2. Hydrogenation of olefins catalyzed by DE-G 1 a/method 2. Substrate Products a (yield) TF b (100%) 1 620 (100%) 1 160 (43%) 1 800 (57%) 2 400 (78%) (22%) 810 230 (100%) (100%) (100%) 1 150 530 130 480 c o hydrogenation - Ergosterol d a Reactions were performed at 25ºC/1 atm H2 and followed by GPC, in the case of styrene and by MR in the other cases. b TF values were determined on basis of the yield of formation of the final product. c The MR data do not allow to determinate the relative quantities of the two isomers formed. d Ergosterol was left under hydrogenation conditions during four days.

Supplementary Material (ESI) for Chemical Communications Synthesis of dendrimers [E.S.I.2] 3 (a) CH 2 =CHCH 2 Br KH, THF, RT, 3d FE (b) hν vis, MeC FE= η 5 -Cp +, PF - 6 (a) HCH 2 (CH 3 ) 2 Cl, Karsted catalyst ether, RT, 13h (b) a 3, DMF 16h, 80ºC 3 3 3 3 3 3 3 3 3 3 3 3 3 CuS 4 sodium ascorbate THF, H 2 RT, 30 min 5 3 3 3 3 3 3 3 3 3 3 3 3 (a) HCH 2 (CH 3 ) 2 Cl Karsted catalyst ether, RT, 13h (b) a 3, DMF 16h, 80ºC 3 3 3 3 3 3 3 3 3 3 CuS 4 sodium ascorbate THF, H 2 RT, 30 min Scheme 1. Synthesis of an 81-allyl dendrimer by Click Chemistry.

Supplementary Material (ESI) for Chemical Communications 3 3 3 3 3 3 3 3 3 CuS 4 sodium ascorbate THF, H 2 rt, 30 min 1-G 0 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 CuS 4 sodium ascorbate THF, H 2 rt, 30 min 2- G 1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 CuS 4 sodium ascorbate THF, H 2 rt, 30 min 3- G 2 Scheme 2. Synthesis of the 1,2,3-triazolylferrocenyl dendrimers by Click Chemistry. General procedure for Click reactions: The azide-dendrimer (1 equiv.) and the alkyne (1.5 equiv. per branch) were dissolved in tetrahydrofuran (THF) and water was added (1:1 THF/water). At 0 C, the CuS 4 was added (1 equiv. per branch, 1M aqueous solution), followed by the dropwise addition of a freshly prepared solution of sodium ascorbate (2 equiv. per branch, 1M aqueous solution). The solution was allowed to stir for 30 min. at room temperature. After removing THF under vacuum, dichloromethane and aqueous solution of ammonia were added. The mixture was

allowed to stir for 10 min in order to remove all the Cu I trapped inside the dendrimer as Cu(H 3 ) + 6. The organic phase was washed twice with water, filtrated under celite and solvent removed under vacuum. The product was washed with pentane in order to remove the excess of alkyne and precipitated using dichloromethane/pentane. rganic dendrimers were obtained as colorless waxy products and ferrocenyl dendrimers were obtained as orange waxy products usually in high yields in both cases. For details of all experimental procedures, characterization data of all products, mass spectra, 1 H RM spectra, cyclic voltammetry conditions and voltammograms of titrations please see reference [E.S.I.2]. [E.S.I.2] C. rnelas, J. Ruiz Aranzaes, E. Cloutet, S. Alves, D. Astruc, Angew. Chem., Int. Ed. Engl. 2007, 46, 872.

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